Storage stable isocyanate-reactive compositions for use in flame-retardant systems

ABSTRACT

This invention relates to stabilizing isocyanate-reactive compositions containing flame retardants by the use of certain tertiary amines or ammonium compounds, in which said stabilized compositions are prepared by mixing 
     (a) at least one isocyanate-reactive compound having a molecular weight of 400 to 10,000 and a functionality of 2 to 7; 
     (b) at least one isocyanate-reactive compound having a molecular weight of less than 399 and a functionality of 2 to 6; 
     (c) at least one (i) isocyanate-reactive tertiary amine polyether, (ii) fatty amido-amine, and/or (iii) ammonium salt derivative of a fatty amido-amine; 
     (d) a flame retardant; 
     (e) a catalyst; and 
     (f) optional additives. 
     This invention also relates to urethane-based products prepared by reaction of organic polyisocyanates with such compositions.

This application is a division of application Ser. No. 08/182,993 filedJan. 14, 1994, now U.S. Pat. No. 5,374,486, which is a divisional ofapplication Ser. No. 08/111,099 filed Aug. 24, 1993, now U.S. Pat. No.5,302,303.

BACKGROUND OF THE INVENTION

This invention relates to storage stable isocyanate-reactivecompositions containing certain tertiary amine or ammonium compoundsthat are useful in the preparation of urethane-based products.

Shelf-life stability of isocyanate-reactive compositions, as measured bychange in reactivity with isocyanates, is often adversely affected bythe addition of flame retardants, especially those based on phosphorus,zinc, antimony, and aluminum. An object of the present invention was toobtain isocyanate-reactive compositions containing flame retardantshaving shelf-life stabilities comparable to or better than those ofcompositions not containing flame retardants. It has now been found thatthe use of certain tertiary amine or ammonium compounds provides suchimproved storage stability.

SUMMARY OF THE INVENTION

This invention relates to storage-stable isocyanate-reactivecompositions containing flame retardants comprising

(a) about 10 to about 90 percent by weight, based on the total ofcomponents (a), (b), (c), (d), and (e), of at least oneisocyanate-reacttve compound having a molecular weight of 400 to about10,000 and a functionality of about 2 to about 7 (preferably 2 to 4);

(b) about 0.6 to about 67 percent by weight, based on the total ofcomponents (a), (b), (c), (d), and (e), of at least oneisocyanate-reactive compound having a molecular weight of less than 399and a functionality of about 2 to about 6 (preferably 2 to 4);

(c) about 0.7 to about 30 percent by weight, based on the total ofcomponents (a), (b), (c), (d), and (e), of a tertiary amine or ammoniumcompound selected from the group consisting of

(i) an isocyanate-reactive tertiary amine polyether having a molecularweight of from about 100 to about 1000 and having the formula

    R[NR.sup.1 R.sup.2 ].sub.m

wherein

R is saturated or unsaturated C₂ -C₈ aliphatic or C₂ -C₈ aliphaticsubstituted with --OH, --SH, or NHR^(a) wherein R^(a) is C₁ -C₈ alkyl orC₂ -C₈ alkenyl; saturated or unsaturated C₅ -C₈ cycloaliphatic or C₅ -C₈cycloaliphatic substituted with C₁ -C₈ alkyl, C₂ -C₈ alkenyl, C₁ -C₈alkylene, --OH, --SH, or NHR^(a) wherein R^(a) is alkyl or alkenyl; orfive- or six-membered aromatic or heteroaromatic optionally substitutedwith C₁ -C₈ alkyl, C₁ -C₈ alkoxy, halogen, cyano, nitro, C₁ -C₈alkylene, --OH, --SH, or NHR^(a) wherein R^(a) is C₁ -C₈ alkyl or C₂ -C₈al kenyl;

R¹ and R² are independently polyether groups terminated withisocyanate-reactive groups selected from --OH, --SH, and NHR^(b) whereinR^(b) is C₁ -C₈ alkyl or C₂ -C₈ alkenyl (preferably hydroxy-terminatedpolyether groups containing polypropylene oxide units); and

m is an integer of from 1 to 4 (preferably 2 to 4);

(ii) a fatty amido-amine;

(iii) an ammonium salt derivative of a fatty amtdo-amine; and

(iv) mixtures thereof;

(d) about 5 to about 55 percent by weight, based on the total ofcomponents (a), (b), (c), (d), and (e), of a flame retardant (preferablycomprising phosphonates, phosphites, phosphates, zinc borates, aluminatrihydrate, antimony oxides, halogen-containing compounds, and mixturesthereof);

(e) about 0.007 to about 6 percent by weight, based on the total ofcomponents (a), (b), (c), (d), and (e), of a catalyst selected fromtertiary amines, organic metal compounds (preferably tin and bismuthcompounds), and mixtures thereof; and

(f) 0 to about 15 percent by weight, based on the total of components(a), (b), (c), (d), and (e), of additives (preferably one or moreblowing agents, acid scavengers, internal mold release agents,surfactants, defoaming agents, and/or water scavengers).

This invention also relates to the method of stabilizingisocyanate-reactive compositions.

This invention further relates to isocyanate addition productscontaining flame retardants prepared by the reaction of suchisocyanate-reactive compositions with organic polyisocyanates.

DETAILED DESCRIPTION OF THE INVENTON

Suitable isocyanate-reactive compounds (a) for use according to thepresent invention having a molecular weight of 400 to about 10,000include compounds containing amino groups, hydroxyl groups, thiolgroups, or a combination thereof. Suitable such compounds includepolyethers, polyesters, polyacetals, polycarbonates, polyesterethers,polyester carbonates, polythioethers, polyamides, polyesteramides,polystloxanes, polybutadienes, and polyacetones, and are described, forexample, in German Offenlegungsschrift 2,832,253 at pages 11 to 20.Particularly preferred isocyanate-reactive compounds contain 2 to 4reactive amino or hydroxyl groups.

Hydroxyl-containing polyethers are suitable for use asisocyanate-reactive component (a). Suitable hydroxyl-containingpolyethers can be prepared, for example, by the polymerization ofepoxides such as ethylene oxide, propylene oxide, butylene oxide,tetrahydrofuran, styrene oxide, or epichlorohydrin, optionally in thepresence of BF₃, or by chemical addition of such epoxides, optionally asmixtures or successively, to starting components containing reactivehydrogen atoms, such as water, alcohols, or amines. Examples of suchstarting components include ethylene glycol, 1,2- or 1,3-propanediol,1,2-, 1,3-, or 1,4-butanediol, glycerin, trimethylolpropane,pentaerythritol, 4,4'-dihydroxydiphenylpropane, aniline, 2,4- or2,6-diaminotoluene, ammonia, ethanolamine, triethanolamine, or ethylenediamine. Sucrose polyethers of the type described, for example, inGerman Auslegeschriften 1,176,358 and 1,064,938 may also be usedaccording to the invention. Polyethers that contain predominantlyprimary hydroxyl groups (up to about 90% by weight, based on all of thehydroxyl groups in the polyether) are also often preferred. Polyethersmodified by vinyl polymers of the kind obtained, for example, by thepolymerization of styrene and acrylonitrile in the presence ofpolyethers (e.g., U.S. Pat. Nos. 3,383,351, 3,304,273, 3,523,093, and3,110,695 and German Patentschrift 1,152,536) are also suitable, as arepolybutadienes containing hydroxyl groups. Particularly preferredpolyethers include polyoxyalkylene polyether polyols, such aspolyoxyethylene diol, polyoxypropylene diol, polyoxybutylene diol, andpolytetramethylene diol.

Hydroxyl-containing polyesters are also suitable for use asisocyanate-reactive component (a). Suitable hydroxyl-containingpolyesters include reaction products of polyhydric alcohols (preferablydiols), optionally with the addition of trihydric alcohols, andpolybasic (preferably dibasic) carboxylic acids. Instead of freepolycarboxylic acids, the corresponding polycarboxylic acid anhydridesor corresponding polycarboxylic acid esters of lower alcohols ormixtures thereof may be used for preparing the polyesters. Thepolycarboxylic acids may be aliphatic, cycloaliphatic, aromatic, orheterocyclic and may be substituted, e.g., by halogen atoms, and/orunsaturated. Suitable polycarboxylic acids include succinic acid, adipicacid, suberic acid, azelaic acid, sebacic acid, phthalic acid,isophthalic acid, trimellitic acid, phthalic acid anhydride,tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride,tetrachlorophthalic acid anhydride, endo-methylene tetrahydrophthalicacid anhydride, glutaric acid anhydride, maleic acid, maleic acidanhydride, fumaric acid, dimeric and trimeric fatty acids, dimethylterephthalic, and terephthalic acid bis-glycol esters. Suitablepolyhydric alcohols include ethylene glycol, 1,2- and 1,3-propanediol,1,4-and 2,3-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentylglycol, 1,3- and 1,4-bis(hydroxymethyl) cyclohexane, 2-methyl-1,3-propanediol, glycerol, trimethylolpropane, 1,2,6-hexanetriol,1,2,4-butanetriol, trimethylolethane, pentaerythritol, quinitol,mannitol, sorbitol, methyl glycoside, diethylene glycol, triethyleneglycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol,polypropylene glycols, dibutylene glycol, and polybutylene glycols. Thepolyesters may also contain a proportion of carboxyl end groups.Polyesters of lactones, such as ε-caprolactone, or of hydroxycarboxylicacids, such as ω-hydroxycaproic acid, may also be used. Hydrolyticallystable polyesters are preferably used in order to obtain the greatestbenefit relative to the hydrolytic stability of the final product.Preferred polyesters include polyesters obtained from adipic acid orisophthalic acid and straight chained or branched diols, as well aslactone polyesters, preferably those based on caprolactone and diols.

Suitable polyacetals include compounds obtained from the condensation ofglycols, such as diethylene glycol, triethylene glycol,4,4'-dihydroxydiphenylmethane, and hexanediol, with formaldehyde or bythe polymerization of cyclic acetals, such as trioxane.

Suitable polycarbonates include those prepared by the reaction of diols,such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethyleneglycol, triethylene glycol, tetraethylene glycol, or thiodiglycol, withphosgene or diaryl carbonates such as diphenyl carbonate (GermanAuslegeschriften 1,694,080, 1,915,908, and 2,221,751; GermanOffenlegungsschrift 2,605,024).

Suitable polyester carbonates include those prepared by the reaction ofpolyester diols, with or without other diols such as 1,3-propanediol,1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol,tetraethylene glycol, or thiodiglycol, with phosgene, cyclic carbonates,or diaryl carbonates such as diphenyl carbonate. Suitable polyestercarbonates more generally include compounds such as those disclosed inU.S. Pat. No. 4,430,484.

Suitable polythioethers include the condensation products obtained bythe reaction of thiodiglycol, either alone or with other glycols,formaldehyde, or amino alcohols. The products obtained arepolythio-mixed ethers, polythioether esters, or polythioether esteramides, depending on the components used.

Suitable polyester amides and polyamides include, for example, thepredominantly linear condensates prepared from polybasic saturated andunsaturated carboxylic acids or the anhydrides thereof and polyvalentsaturated or unsaturated amino alcohols, diamines, polyamine$, andmixtures thereof.

Although less preferred, other suitable hydroxyl-containing compoundsinclude polyhydroxyl compounds already containing urethane or ureagroups and modified or unmodified natural polyols. Products of additionof alkylene oxides to phenol-formaldehyde resins or to urea-formaldehyderesins are also suitable. Furthermore, amide groups may be introducedinto the polyhydroxyl compounds as described, for example, in GermanOffenlegungsschrift 2,559,372.

Polyhydroxyl compounds in which polyadducts or polycondensates orpolymers are present in a finely dispersed or dissolved form may also beused according to the invention, provided that the molecular weightsrange from about 400 to about 10,000. Polyhydroxyl compounds of thistype may be obtained, for example, by carrying out polyadditionreactions (e.g., reactions between polyisocyanates and amino functionalcompounds) or polycondensation reactions (e.g., between formaldehyde andphenols or amines) in situ in the abovementioned hydroxyl-containingcompounds. Processes of this type are described, for example, in GermanAuslegeschriften 1,168,075 and 1,260,142 and GermanOffenlegungsschriften 2,324,134, 2,423,984, 2,512,385, 2,513,815,2,550,796, 2,550,797, 2,550,833, 2,550,862, 2,633,293, and 2,639,254.Suitable compounds may also be obtained according to U.S. Pat. Nos.3,869,413 or 2,550,860 by mixing a previously prepared aqueous polymerdispersion with a polyhydroxyl compound and then removing water from themixture.

Polyhydroxyl compounds modified with vinyl polymers, such as thoseobtained, for example, by the polymerization of styrene andacrylonitrile in the presence of polycarbonate polyols (GermanPatentschrift 1,769,795 and U.S. Pat. No. 3,637,909) are also suitablefor the process of the invention.

General discussions of representative hydroxyl-containing compounds thatmay be used according to the present invention can be found, forexample, in Polyurethanes, Chemistry and Technology by Saunders andFrisch, Interscience Publishers, New York, London, Volume I, 1962, pages32-42 and pages 44-54, and Volume II, 1964, pages 5-6 and 198-199, andin Kunststoff-Handbuch, Volume VII, Vieweg-Hochtlen, Carl-Hanser-Verlag,Munich, 1966, on pages 45 to 71.

Suitable isocyanate-reactive compounds containing amino groups includethe so-called amine-terminated polyethers containing primary orsecondary (preferably primary) aromatically or aliphatically (preferablyaliphatically) bound amino groups. Compounds containing amino end groupscan also be attached to the polyether chain through urethane or estergroups. These amine-terminated polyethers can be prepared by any ofseveral methods known in the art. For example, amine-terminatedpolyethers can be prepared from polyhydroxyl polyethers (e.g.,polypropylene glycol ethers) by a reaction with ammonia in the presenceof Raney nickel and hydrogen (Belgian Patent 634,741). Polyoxyalkylenepolyamines can be prepared by a reaction of the corresponding polyolwith ammonia and hydrogen in the presence of a nickel, copper, chromiumcatalyst (U.S. Pat. No. 3,654,370). The preparation of polyetherscontaining amino end groups by the hydrogenation of cyanoethylatedpolyoxypropylene ethers is described in German Patentschrift 1,193,671.Other methods for the preparation of polyoxyalkylene (polyether) aminesare described in U.S. Pat. Nos. 3,155,728 and 3,236,895 and in FrenchPatent 1,551,605. French Patent 1,466,708 discloses the preparation ofpolyethers containing secondary amino end groups. Also useful are thepolyether polyamines described in U.S. Pat. Nos. 4,396,729, 4,433,067,4,444,910, and 4,530,941.

Relatively high molecular weight polyhydroxy-polyethers suitable for thepresent invention may be converted into the corresponding anthranilicacid esters by reaction with isatoic acid anhydride. Methods for makingpolyethers containing aromatic amino end groups are disclosed in GermanOffenlegungsschriften 2,019,432 and 2,619,840 and U.S. Pat. Nos.3,808,250, 3,975,428, and 4,016,143. Relatively high molecular weightcompounds containing amino end groups may also be obtained according toGerman Offenlegungsschrift 2,546,536 or U.S. Pat. No. 3,865,791 byreacting isocyanate prepolymers based on polyhydroxyl polyethers withhydroxyl-containing enamines, aldimines, or ketimines and hydrolyzingthe reaction product.

Aminopolyethers obtained by the hydrolysis of compounds containingisocyanate end groups are also preferred amine-terminated polyethers.For example, in a process disclosed in German Offenlegungsschrift2,948,419, polyethers containing hydroxyl groups (preferably two orthree hydroxyl groups) react with polyisocyanates to form isocyanateprepolymers whose isocyanate groups are then hydrolyzed in a second stepto amino groups. Preferred amine-terminated polyethers are prepared byhydrolyzing an isocyanate compound having an isocyanate group content offrom 0.5 to 40% by weight. The most preferred polyethers are prepared byfirst reacting a polyether containing two to four hydroxyl groups withan excess of an aromatic polyisocyanate to form an isocyanate terminatedprepolymer and then converting the isocyanate groups to amino groups byhydrolysis. Processes for the production of useful amine-terminatedpolyethers using isocyanate hydrolysis techniques are described in U.S.Pat. Nos. 4,386,218, 4,456,730, 4,472,568, 4,501,873, 4,515,923,4,525,534, 4,540,720, 4,578,500, and 4,565,645, European PatentApplication 97,299, and German Offenlegungsschrift 2,948,419, all thedisclosures of which are herein incorporated by reference. Similarproducts are also described in U.S. Pat. Nos. 4,506,039, 4,525,590,4,532,266, 4,532,317, 4,723,032, 4,724,252, 4,855,504, and 4,931,595.

Other suitable amine-terminated polyethers includeaminophenoxy-substituted polyethers described, for example, in EuropeanPatent Applications 288,825 and 268,849 and U.S. application Ser. No.07/266,725 (filed Nov. 3, 1988).

The amine-terminated polyethers used in the present invention are inmany cases mixtures with other isocyanate-reactive compounds having theappropriate molecular weight. These mixtures generally should contain(on a statistical average) two to four isocyanate reactive amino endgroups.

Aminocrotonate-terminated derivatives of polyethers, as well as of otherpolyols described above, can be prepared from acetoacetate-modifiedpolyethers as described, for example, in U.S. Pat. Nos. 5,066,824, and5,151,470.

Suitable isocyanate-reactive compounds (b) have a molecular weight ofless than 399 and a functionality of about 2 to about 6 (preferably 2 to4) and are often referred to as chain extenders (functionality of about2) or crosslinkers (functionality greater than 2). Such compoundscontain hydroxyl groups, amino groups, thiol groups, or a combinationthereof, and generally contain 2 to 8 (preferably 2 to 4)isocyanate-reactive hydrogen atoms.

The preferred hydroxyl-containing chain extenders and crosslinkersinclude glycols and polyols, such as 1,2-ethanediol, 1,2- and1,3-propylene glycol, 1,4- and 2,3-butylene glycol, 1,6-hexanediol,1,8-octanediol, neopentyl glycol, cyclohexanedimethanol,1-methyl-l,3-propanediol, 2-methyl-l,3-propanediol, glycerol,trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol,1,2,4-butanetriol, and trimethylolethane.

Suitable chain extenders (b) also include hydroxyl-containing polyethershaving a molecular weight of less than 399. Suitable hydroxyl-containingpolyethers can be prepared, for example, by the methods discussed abovefor the hydroxy-containing polyethers of component (a) except that onlylower molecular weight polyethers are used for component (b).Particularly suitable polyethers include polyoxyalkylene polyetherpolyols, such as polyoxyethylene diol, polyoxypropylene diol,polyoxybutylene diol, and polytetramethylene diol having the requisitemolecular weights.

Amine chain extenders preferably contain exclusively aromatically boundprimary or secondary (preferably primary) amino groups and preferablyalso contain alkyl substituents. Examples of such aromatic diaminesinclude 1,4-diaminobenzene, 2,4- and/or 2,6-diaminotoluene, meta-xylenediamine, 2,4'-and/or 4,4'-diaminodiphenylmethane,3,3'-dimethyl-4,4'-diaminodiphenylmethane,1-methyl-3,5-bis(methylthio)-2,4- and/or -2,6-diaminobenzene,1,3,5-triethyl-2,4-diaminobenzene,1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-and/or-2,6-diaminobenzene, 4,6-dimethyl-2-ethyl-l,3-diaminobenzene,3,5,3',5'-tetraethyl-4,4-diaminodiphenylmethane,3,5,3',5'-tetraisopropyl-4,4'-diaminodiphenylmethane, and3,5-diethyl-3',5'-diisopropyl-4,4'-diaminodiphenylmethane. Althoughgenerally less preferred, certain (cyclo)aliphatic diamines are alsosuitable. A particularly suitable (cyclo)aliphatic diamine is1,3-bis(aminomethyl)cyclohexane. Such diamines may, of course, also beused as mixtures.

Suitable tertiary amine or ammonium compounds of component (c) includeisocyanate-reactive tertiary amine polyethers, fatty amido-amines,ammonium derivatives of fatty amido-amines, and mixtures thereof.

Suitable isocyanate-reactive tertiary amine polyethers (c)(i) includecompounds having the formula

    R[NR.sup.1 R.sup.2 ].sub.m

wherein R, R¹, R², and m have the meanings given above.

The term "saturated or unsaturated C₂ -C₈ aliphatic" as applied to groupR of component (c)(i) refers to straight or branched chain hydrocarbongroups having from 2 to 8 carbon atoms attached to from 1 to 4 --NR¹ R²groups (preferably such that no carbon atom is attached to two nitrogenatoms) and optionally containing carbon-carbon double bonds (with theproviso that no double-bonded carbon atom is attached directly to anitrogen atom). For example, when m is 2, saturated or unsaturated C₂-C₈ aliphatic groups include linear ethylene, propylene, butylene,pentylene, hexylene, heptylene, and octylene groups, as well as theisomertc branched forms thereof. The term "saturated or unsaturated C₅-C₈ cycloaliphatic" as applied to group R of component (c)(i) refers tocyclopentane, cyclohexane, cycloheptane, and cyclooctane groups, as wellas to C₁ -C₈ alkyl derivatives thereof, that are attached to the --NR¹R² groups either directly to the ring carbon atoms or indirectly throughthe optional C₁ -C₈ alkylene substituents (preferably such that nocarbon atom is attached directly to two nitrogen atoms) and thatoptionally contain carbon-carbon double bonds in the cyclic moiety(preferably such that no double-bonded carbon atom is attached directlyto a nitrogen atom). For example, when m is 2, preferred saturated orunsaturated C₅ -C₈ cycloaliphatic groups include the various isomericcyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene groups.Suitable but less preferred saturated or unsaturated C₅ -C₈ cycloaliphatic groups include those in which at least one ring carbon atom isattached to the --NR¹ R² groups indirectly through an optional C₁ -C₈alkylene substituent, such as groups in which m is 2 having the formulas##STR1## and the like. The term "five- or six-membered aromatic orheteroaromatic" as applied to group R of component (c)(i) refers tobenzene, six-membered heterocyclic groups containing at least one ringnitrogen atom (such as pyridine, pyrazine, pyrimidine, pyridazine, andthe like), and five-membered heterocyclic groups containing at least onering nitrogen, oxygen, or sulfur atom (such as, furan, pyrrole,imidazole, pyrazole, thiophene, oxazole, isoxazole, thiazole,isothiazole, and the like), each of which can be substituted with C₁ -C₈alkyl, C₁ -C₈ alkoxy, halogen, cyano, nitro, or C₁ -C₈ alkylene. Whenthe substituent is C₁ -C₈ alkylene, the aromatic or heteroaromatic groupcan be attached to the --NR¹ R² groups indirectly through the alkylenesubstituents.

Each group R can optionally be substituted with --OH, --SH, or --NHR^(a)groups wherein R^(a) is C₁ -C₈ alkyl or C2-C₈ alkenyl (preferablyalkenyl in which no double-bonded carbon atom is attached directly to anitrogen atom), particularly when m is 1, to provide additionalisocyanate-reactive sites. Examples of suitable such groups R when m is1 include hydroxyethyl and hydroxypropyl. Such groups are generally notpreferred when m is 2, 3, or 4.

The term "polyether groups terminated with isocyanate-reactive groups"as applied to groups R¹ and R² of component (c)(i) refers to polyethersprepared, for example, by the general methods described above forpreparing isocyanate-reactive component (a), provided that one end ofeach polyether chain is attached to the nitrogen atom indicated in theformula and the other end is terminated by at least one --OH, --SH, orNHR^(b) group and further provided that the molecular weight of theresultant tertiary amine polyether (c)(i) ranges from about 100 to about1000. Suitable polyethers include hydroxy-terminated polyoxyalkylenepolyethers, such as those having polyoxyethylene, polyoxypropylene,polyoxybutylene, or polytetramethylene groups, especiallyhydroxy-terminated polyoxyethylene groups.

Particularly preferred isocyanate-reactive tertiary amine polyethers(c)(i) are those in which R is a difunctional saturated C₂ -C₈ aliphaticgroup, R¹ and R² are independently hydroxy-terminated polyetherscontaining exclusively polypropylene oxide units, and m is 2, and inwhich the molecular weight is from 200 to 600.

Suitable fatty amido-amines (c)(ii) include amides of a saturated orunsaturated C₁₂ -C₂₄ fatty acid and a di-, tri-, or tetraaminoalkane(preferably an N-alkylated diaminoalkane) having at least one amidenitrogen atom and at least one basic amino group. It is also possible,although less preferred, to use fatty amido-amines having hydroxylsubstituents. Preferred fatty amtdo-amtnes are compounds having thegeneral formula

    R.sup.a --CO--NR.sup.c --R.sup.b --NR.sup.d R.sup.e

wherein R^(a) is C₁₁ -C₂₃ alkyl, alkenyl, alkadienyl, or alkatrienyl,R^(b) is C₂ -C₈ alkylene or alkenylene, and R^(c) R^(d) and R^(e) areindependently hydrogen or C₁ -C₈ alkyl (preferably those in which R^(c)is hydrogen and R^(d) and R^(e) are both C₁ -C₈ alkyl). Suitable fattyamido-amines of this type include those in which R^(a) is derived fromstearic acid, commercial coconut fatty acid mixtures, tallow ortrain-oil fatty acids, commercial paraffin fatty acids (includingmixtures thereof), undecylenic acid, oleic acid, linoleic acid, tall oilfatty acids, ricinoleic acid, and the like. A particularly preferredfatty amido-amine is cocamidopropyldimethylamine (available as ADOGENK-14 from Witco Corporation).

Suitable ammonium derivatives of fatty amido-amines (c)(iii) includefatty amido-amines (such as, for example, those described above forcomponent (c)(ii)) in which at least one basic amino group is protonatedor quaternized (for example, to form an N,N,N-trialkylamino group).Preferred ammonium derivatives of fatty amido-amines are compoundshaving the general formula

    R.sup.a --CO--NR.sup.c --R.sup.b --NR.sup.d R.sup.e R.sup.f+  X.sup.-

wherein R^(a) is C₁₁ -C₂₃ alkyl, alkenyl, alkadienyl, or alkatrienyl,R^(b) is C₂ -C₈ alkylene or alkenylene, R^(c) is hydrogen or C₁ -C₈alkyl, R^(d) and R^(e) are independently C₁ -C₈ alkyl, R^(f) is hydrogenor Ci-C₈ alkyl, and X⁻ is any suitable counterion (such as halide,sulfate or sulfonate, phosphate or phosphonate, or carboxylate).Suitable ammonium derivatives of this type include those in which R^(a)is derived from steartc acid, commercial coconut fatty acid mixtures,tallow or train-oil fatty acids, commercial paraffin fatty acids(including mixtures thereof), undecylenic acid, oleic acid, linoleicacid, tall oil fatty acids, ricinoleic acid, and the like. Particularlypreferred ammonium derivatives are the protonated ammonium salts ofamides prepared from oleic acid or tall oil fatty acids and3-(dimethylamino)propylamine in which X⁻ is the corresponding fatty acidcarboxylate. E.g., U.S. Pat. No. 3,726,952.

Isocyanate-reactive tertiary amine polyethers (c)(i) are particularlypreferred for use as component (c). It is also often desirable to use atertiary amine polyether (c)(i) in combination with a smaller amountfatty amido-amine (c)(ii) and/or an ammonium derivative (c)(iii).

Suitable flame retardants (d) (which, as the term is used herein, alsoinclude smoke suppressants and other known combustion modifiers),include phosphonates, phosphites, and phosphates (such as dimethylmethylphosphonate, ammonium polyphosphate, and various cyclic phosphateand phosphonate esters known in the art); halogen-containing compoundsknown in the art (such as brominated diphenyl ether and other brominatedaromatic compounds); melamine; antimony oxides (such as antimonypentoxide and antimony trioxide); zinc compounds (such as various knownzinc borates); aluminum compounds (such as alumina trihydrate); andmagnesium compounds (such as magnesium hydroxide).

Suitable catalysts (e) include tertiary amines and metal compounds knownin the art. Suitable tertiary amine catalysts include triethylamine,tributylamine, N-methylmorphol ine, N-ethylmorphol ine,N,N,N',N'-tetramethylethylene diamine, pentamethyldiethylene triamtne,and higher homologs (German Offenlegungsschriften 2,624,527 and2,624,528), 1,4-diazabicyclo[2.2.2]octane,N-methyl-N'-(dimethylaminoethyl)piperazine,bis(dimethylaminoalkyl)piperazines (German Offenlegungsschrift2,636,787), N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine,N,N-diethylbenzylamine, bis(N,N-diethylaminoethyl) adipate,N,N,N',N'-tetramethyl-1,3-butanediamine,N,N-dimethyl-β-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole, monocycl ic and bicycl ic amidines (GermanOffenlegungsschrift 1,720,633), bis(dialkylamino)alkyl ethers (U.S. Pat.No. 3,330,782, German Auslegeschrift 030,558, and GermanOffenlegungsschriften 1,804,361 and 2,618,280), and tertiary aminescontaining amide groups (preferably formamide groups) according toGerman Offenlegungsschriften 2,523,633 and 2,732,292. The catalysts usedmay also be the known Mannich bases of secondary amines (such asdimethylamine) and aldehydes (preferably formaldehyde) or ketones (suchas acetone) and phenols.

Suitable catalysts also include certain tertiary amines containingisocyanate reactive hydrogen atoms. Examples of such catalysts includetriethanolamine, triisopropanolamine, N-methyldiethanolamine,N-ethyldiethanolamine, N,N-dimethylethanolamine, their reaction productswith alkylene oxides (such as propylene oxide and/or ethylene oxide) andsecondary-tertiary amines according to German Offenlegungsschrift2,732,292.

Other suitable catalysts include organic metal compounds, especiallyorganic tin, bismuth, and zinc compounds. Suitable organic tin compoundsinclude those containing sulfur, such as dioctyl tin mercaptide (GermanAuslegeschrift 1,769,367 and U.S. Pat. No. 3,645,927), and, preferably,tin(II) salts of carboxylic acids, such as tin(II) acetate, tin(II)octoate, tin(II) ethylhexoate, and tin(II) laurate, as well as tin(IV)compounds, such as dibutyltin dilaurate, dibutyltin dichloride,dibutyltin diacetate, dibutytin maleate, and dioctyltin diacetate.Suitable bismuth compounds include bismuth neodecanoate, bismuthversalate, and various bismuth carboxylates known In the art. Suitablezinc compounds include zinc neodecanoate and zinc versalate. Mixed metalsalts containing more than one metal (such as carboxylic acid saltscontaining both zinc and bismuth) are also suitable catalysts.

Any of the above-mentioned catalysts may, of course, be used asmixtures.

Further representatives of catalysts to be used according to theinvention and details concerning their mode of action are described inKunststoff Handbuch, Volume VII, published by Vieweg and Hochtlen,Carl-Hanser-Verlag, Munich, 1966, for example, on pages 96 to 102.

Suitable additives (f) may optionally also be used in the preparation ofthe compositions of the invention and include, for example, blowingagents, internal mold release agents, surfactants, acid scavengers,water scavengers, cell regulators, defoaming agents, deaeraters,pigments, dyes, UV stabilizers, plasticizers, fungistatic orbacteriostatic substances, and fillers, such as those described inEuropean Patent Application 81,701 at column 6, line 40, to column 9,line 31. When used, the preferred additives include blowing agents,internal mold release agents, acid scavengers, water scavengers,defoaming agents, and surfactants.

Suitable blowing agents for use in the preparation of polyurethane foamsinclude water and/or readily volatile organic substances. Organicblowing agents include acetone, ethyl acetate, methanol, ethanol,low-boiling hydrocarbons (such as butane, hexane, or heptane) orfluorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons, or otherhalogen-substituted alkanes (such as methylene chloride, chloroform,ethyl idene chloride, vinyl idene chloride, monofluorotrichloromethane,chlorodifluoromethane, and dichlorodifluoromethane), diethyl ether, orcarboxylic acids (such as lactic acid, citric acid, and malonic acid),as well as carbon dioxide generated by the hydrolysis of isocyanategroups. A blowing effect may also be obtained by adding compounds whichdecompose at temperatures above room temperature and thereby give offgases such as nitrogen (for example, azo compounds such asazoisobutyronitrile or carbon dioxide (such as dimethyl dicarbonate).Other examples of blowing agents and information on their use can befound in Kunststoff-Handbuch, Volume VII, Vieweg-Hochtlen,Carl-Hanser-Verlag, Munich, 1966, for example, on pages 108-109,453-455, and 507-510.

Internal mold release agents are compounds that are added to thereactive components of the isocyanate addition reaction, usually theisocyanate-reactive component, to assist in the removal of apolyurethane product from a mold. Suitable internal mold release agentsfor the present invention include those based at least in part on fattyacid esters (e.g., U.S. Pat. Nos. 3,726,952, 3,925,527, 4,058,492,4,098,731, 4,201,847, 4,254,228, 4,868,224, and 4,954,537 and BritishPatent 1,365,215); metal and/or amine salts of carboxylic acids, amidocarboxylic acids, phosphorus-containing acids, or boron-containing acids(e.g., U.S. Pat. Nos. 4,519,965, 4,581,386, 4,585,803, 4,876,019, and4,895,879); polysiloxanes (e.g., U.S. Pat. No. 4,504,313); amidines(e.g., U.S. Pat. Nos. 4,764,540, 4,789,688, and 4,847,307); resinsprepared by the reaction of isocyanate prepolymers and apolyamine-polyimine component (e.g., U.S. Pat. No. 5,198,508); andneutralized esters prepared from certain amine-started tetrahydroxycompounds described In U.S. Pat. No. 5,208,268.

Surfactants (or surface-active agents) include emulsifiers and foamstabilizers. Examples of suitable surfactants include any of severalsilicone surfactants known in the art (including, for example, thoseavailable commercially from Dow Corning Corporation, Union CarbideChemical and Plastics Co., Inc., and Rhein Chemie Corporation), as wellas various amine salts of fatty acids (such as diethylamine oleate ordiethanolamine stearate) and sodium salts of ricinoleic acids.

Acid scavengers are compounds that control the acidity and waterconcentration of the compositions of the invention. Preferred acidscavengers include various orthoesters (such as trimethyl orthoformate),carbodiimides (such as 2,2',6,6'-tetratsopropyldtphenylcarbodiimidesavailable as STABOXAL I and STABOXAL P from Rhein Chemie Corp.), andepoxides (such as 3,4-epoxycyclohexylmethyl3,4-epoxycyclohexylcarboxylate, available as ERL-4221 from UnionCarbide).

Water scavengers (or moisture scavengers) are compounds that maintain alow water content in the compositions of the invention. Suitable waterscavengers are described, for example, in U.S. Pat. Nos. 3,755,222 and4,695,618. Examples of suitable water scavengers includealkalialuminosilcates (available as BAYLITH L, BAYLITH T, and BAYLITH Wpowders or pastes from Bayer AG, Germany) and chemically reacting waterscavengers (such as ZOLDINE MS-Plus from Angus Chemical Company).

Defoaming agents are compounds known in the art, especially for use withcoatings, that inhibit foaming during preparation of the ultimate.isocyanate addition products. Examples of suitable defoaming agentsinclude polysiloxanes (such as dimethyl polysiloxane, polysiloxanepolyether copolymers, and modified polymethylsiloxanes) and emulsifiablepetroleum oils known in the art.

Known fillers and/or reinforcing substances, such as barium sulfate,calcium carbonate, calcium silicate, clays, kieselguhr, whiting, mica,and especially glass fibers, liquid crystal fibers, glass flakes, glassballs, microspheres, aramide fibers, and carbon fibers, are alsosuitable.

The storage-stable isocyanate-reactive compositions of the presentinvention can be prepared by mixing the individual components in anyorder but are preferably prepared by first mixing components (a), (b),and (c), followed by adding in sequence components (d), (f), and (e).

The isocyanate-reactive compositions of the present invention containcertain tertiary amine or ammonium compounds (preferablyisocyanate-reactive tertiary amine polyethers) that confer storagestability on the compositions, even when flame retardants are present.Such isocyanate-reactive compositions can be used for the preparation ofvarious urethane-based products by methods known in the art, such asreaction injection molding ("RIM"), resin transfer molding ("RTM"), castmolding, open pour molding, and spraying. Polyurethane systems based onthe compositions of the present invention can be formulated for thepreparation of microcellular or non-microcellular rigid polyurethanes,microcellular or non-microcellular elastomeric polyurethanes, includingintegral skin or non-skinning polyurethanes. As used herein, the term"polyurethane" also refers to polyureas and polyurethane polyureahybrids.

When preparing polyurethanes according to the invention by theisocyanate addition reaction, the storage-stable isocyanate-reactivecompositions of this invention are allowed to react with organicpolyisocyanates known in the art. Suitable polyisocyanates can beunmodified isocyanates, modified polyisocyanates, or isocyanateprepolymers. Suitable organic polyisocyanates include aliphatic,cycloaliphatic, araliphatic, aromatic, and heterocyclic polyisocyanatesof the type described, for example, by W. Siefken in Justus LiebigsAnnalen der Chemie, 562, pages 75 to 136. Such isocyanates include thosehaving the formula

    Q(NCO).sub.n

in which n is a number from 2 to about 5 (preferably 2 to 3) and Q is analiphatic hydrocarbon group containing 2 to about 18 (preferably 6 to10) carbon atoms, a cycloaliphatic hydrocarbon group containing 4 toabout 15 (preferably 5 to 10) carbon atoms, an araliphatic hydrocarbongroup containing 8 to 15 (preferably 8 to 13) carbon atoms, or anaromatic hydrocarbon group containing 6 to about 15 (preferably 6 to 13)carbon atoms. Examples of suitable tsocyanates include ethylenediisocyanate; 1,4-tetramethylene diisocyanate; 1,6-hexamethylenediisocyanate; 1,12-dodecane diisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,3- and -1,4-diisocyanate, and mixtures of these isomers;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane ("isophoronediisocyanate"; see, e.g. German Auslegeschrift 1,202,785 and U.S. Pat.No. 3,401,190); 2,4- and 2,6-hexahydrotoluene diisocyanate and mixturesof these isomers; dicyclohexylmethane-4,4'-diisocyanate ("hydrogenatedMDI", or "HMDI"); 1,3- and 1,4-phenylene diisocyanate; 2,4- and2,6-toluene diisocyanate and mixtures of these isomers ("TDI");diphenylmethane-2,4'and/or-4,4'-diisocyanate ("MDI");naphthylene-1,5-diisocyanate; triphenyl-methane-4,4',4"-triisocyanate;polyphenyl-polymethylene-polyisocyanaates of the type which may beobtained by condensing aniline with formaldehyde, followed byphosgenation ("crude MDI"), which are described, for example, in BritishPatents 878,430 and 848,671; norbornane diisocyanates, such as describedin U.S. Pat. No. 3,492,330; m- and p-isocyanatophenylsulfonylisocyanates of the type described in U.S. Pat. No. 3,454,606;perchlorinated aryl polyisocyanates of the type described, for example,in U.S. Pat. No. 3,227,138; modified polyisocyanates containingcarbodiimide groups of the type described in U.S. Pat. No. 3,152,162;modified polyisocyanates containing urethane groups of the typedescribed, for example, in U.S. Pat. Nos. 3,394,164 and 3,644,457;modified polyisocyanates containing allophanate groups of the typedescribed, for example, in British Patent 994,890, Belgian Patent761,616, and published Dutch Patent Application 7,102,524; modifiedpolyisocyanates containing isocyanurate groups of the type described,for example, in U.S. Pat. No. 3,002,973, German Patentschriften1,022,789, 1,222,067 and 1,027,394, and German Offenlegungsschriften1,919,034 and 2,004,048; modified polyisocyanates containing urea groupsof the type described in German Patentschrift 1,230,778; polyisocyanatescontaining biuret groups of the type described, for example, in GermanPatentschrift 1,101,394, U.S. Pat. Nos. 3,124,605 and 3,201,372, and inBritish Patent 889,050; polyisocyanates obtained by telomerizationreactions of the type described, for example, in U.S. Pat. No.3,654,106; polyisocyanates containing ester groups of the typedescribed, for example, in British Patents 965,474 and 1,072,956,in U.S.Pat. No. 3,567,763, and in German Patentschrift 1,231,688; reactionproducts of the above-mentioned isocyanates with acetals as described inGerman Patentschrift 1,072,385; and polyisocyanates containing polymericfatty acid groups of the type described in U.S. Pat. No. 3,455,883. Itis also possible to use the isocyanate-containing distillation residuesaccumulating in the production of isocyanates on a commercial scale,optionally in solution in one or more of the polyisocyanates mentionedabove. It is also possible to use mixtures of the polyisocyanatesdescribed above.

In general, it is preferred to use readily available polyisocyanates,such as 2,4- and 2,6-toluene diisocyanates and mixtures of these isomers("TDI"); polyphenyl-polymethylenepolyisocyanates of the type obtained bycondensing aniline with formaldehyde, followed by phosgenation ("crudeMDI"); and polyisocyanates containing carbodiimide groups, urethanegroups, allophanate groups, isocyanurate groups, urea groups, or biuretgroups ("modified polyisocyanates").

It is, of course, also possible to use isocyanate prepolymers preparedby reaction of any of the above polyisocyanates with a substoichiometricamount of an isocyanate-reactive compound such as, for example, thosedescribed above for component (a).

Regardless of the particular type of polyurethane product that is to beprepared, the polyurethane-forming reaction components (that is, theisocyanate-reactive component and the isocyanate component) may beallowed to react, for example, by one-stage reactions, prepolymerreactions, or semiprepolymer reactions. Suitable techniques includereaction injection molding ("RIM"), resin transfer molding ("RTM"), castmolding, open pour molding, and spraying. Machines, such as thosedescribed in U.S. Pat. No. 2,764,565, may be used in many of theseprocesses. Particulars of the processing machines which may also be usedto produce polyurethanes according to the invention may be found inKunststoff-Handbuch, Vol. VII, Vieweg and Hochtlen, Carl-Hanser-Verlag,Munich 1966, pages 121 to 205.

When carrying out a reaction of an isocyanate-reactive compositionaccording to the invention with an isocyanate, the quantity ofisocyanate component should preferably be such that the isocyanate indexis from 80 to 130. By "isocyanate index" is meant the quotient of thenumber of isocyanate groups divided by the number of isocyanate-reactivegroups, multiplied by 100. For example, when preparing a rigidpolyurethane foam, the isocyanate index is preferably from 100 to 120.On the other hand, when preparing a polyurethane elastomer, theisocyanate index is preferably from 90 to 110. When using anisocyanate-reactive composition according to the invention for spraying,the isocyanate index is preferably from 90 to 120.

Molded foams prepared using the compositions of the present inventionmay be prepared by introducing the reaction mixture into a suitablemold. Suitable mold materials include metals (for example, aluminum orsteel) or plastics (for example, unsaturated polyester resin or epoxideresin). In the mold, the foamable reaction mixture foams to form themolded product. In-mold foaming may be carried out in such a way thatthe molding has a compact skin and a cellular core. It is possible tointroduce into the mold a quantity of foamable reaction mixture suchthat the foam formed just fills the mold. It is also possible tointroduce into the mold more foamable reaction mixture than is requiredto fill the interior of the mold with foam, technique known as"over-charging" and described, for example, in U.S. Pat. Nos. 3,178,490and 3,182,104.

Spray systems are, of course, applied to suitable substrates using knownspray apparatus, such as those described in U.S. Pat. No. 2,764,565.Details concerning processing apparatus that may be used according tothe invention may be found in Kunststoff-Handbuch, Vol. VII, Vieweg andHochtlen, Carl-Hanser-Verlag, Munich 1966. High pressure equipmenthaving the ability to heat the components is generally used for theapplication of spray systems. The pressure required is generally about 7to 11 Mpa, with throughput of about 3 to 10 kg per minute. The organicpolyisocyanate and isocyanate-reactive compositions according to theinvention are mixed and sprayed using a spray gun equipped for static,impingement, or dynamic mixing. Suitable two-component spray pumps andguns are manufactured by, for example, Binks Manufacturing Company,Gusmer (PMC, Inc.), Graco Inc., Glass Craft Inc., TAH Industries, andUnipre GmbH.

Although any of the isocyanate-reactive compositions of the inventionexhibit improved storage stability, the relative amounts of the variousreactive components and additives can dramatically affect the physicalproperties obtained. Thus, each type of desired product and method ofapplication typically employs a more narrowly defined range ofquantities for each of the components.

For example, in the preparation of rigid microcellular ornon-microcellular urethane-based products, preferred isocyanate-reactivecompositions of the invention contain 18 to 57 percent by weight (morepreferably 21 to 48 percent by weight) of isocyanate-reactive component(a); 28 to 67 percent by weight (more preferably 35 to 62 percent byweight) of chain extender or crosslinker (b); 1.4 to 27 percent byweight (more preferably 2 to 23 percent by weight) of component (c); 10to 38 percent by weight (more preferably 10 to 24 percent by weight) offlame retardant (d); and 0.07 to 3.5 percent by weight (more preferably0.2 to 2 percent by weight) of catalyst (e), all amounts being based onthe total amount of components (a), (b), (c), (d), and (e). When thepreferred isocyanate-reactive component (a) includes a polyamine oraminocrotonate-terminated polyether, component (c) is preferably 3 to 24percent by weight (more preferably 3 to 19 percent by weight and mostpreferably 3 to 14 percent by weight) of an isocyanate-reactive tertiaryamine polyether (c)(i) and may optionally also contain as a secondcomponent 0.7 to 14 percent by weight (more preferably 1 to 11 percentby weight and most preferably 2 to 9 percent by weight) of a fattyamido-amine (c)(ii). When the preferred isocyanate-reactive component(a) does not include a polyamine or aminocrotonate-terminated polyether,component (c) is also preferably an isocyanate-reactive tertiary aminepolyether (c)(i) (in the quantities listed immediately above) but thepreferred optional second component is an ammonium salt derivative of afatty amido-amine (c)(iii) (preferably 3 to 24 percent by weight, morepreferably 3 to 19 percent by weight, and most preferably 3 to 14percent by weight). Although chain extenders and crosslinkers containingamino and thiol groups can be used, chain extenders and crosslinkerscontaining hydroxyl groups are preferred. Preferred flame retardants areliquid for processing ease and include, for example, dimethylmethylphosphonate or ANTIBLAZE NR-25, but solid flame retardants canalso be effective. Limitations on the physical state of the flameretardant are, in general, determined by equipment processingcapabilities. Preferred catalysts include tin (especially tin (IV))compounds and N,N-dimethylcyclohexylamine. Additives, if used at all,preferably include 0 to 3 percent by weight of a blowing agent, 0 to 2.5percent by weight of an acid scavenger, 0 to 10 percent by weight of aninternal mold release agent, 0 to 3 percent by weight of a surfactant, 0to 1 percent by weight of a defoaming agent, and 0 to 5 percent byweight of a water scavenger.

In the preparation of microcellular and non-microcellular urethane-basedelastomers, preferred lsocyanate-reactive compositions of the inventioncontain 32 to 90 percent by weight (more preferably 50 to 76 percent byweight) of isocyanate-reactive component (a); 0.7 to 38 percent byweight (more preferably 3 to 24 percent by weight) of chain extender orcrosslinker (b); 1.4 to 27 percent by weight (more preferably 2 to 23percent by weight) of component (c); 20 to 48 percent by weight (morepreferably 25 to 48 percent by weight) of flame retardant (d); and 0.07to 3.5 percent by weight (more preferably 0.2 to 2 percent by weight) ofcatalyst (e), all amounts being based on the total amount of components(a), (b), (c), (d), and (e). When the preferred isocyanate-reactivecomponent (a) includes a polyamine or aminocrotonate-terminatedpolyether, component (c) is preferably 3 to 24 percent by weight (morepreferably 3 to 19 percent by weight and most preferably 3 to 14 percentby weight) of an isocyanate-reactive tertiary amine polyether (c)(i) andmay optionally also contain as a second component 0.7 to 14 percent byweight (more preferably 1 to 11 percent by weight and most preferably 2to 9 percent by weight) of a fatty amido-amine (c)(ii). When thepreferred isocyanate-reactive component (a) does not include a polyamineor aminocrotonate-terminated polyether, component (c) is also preferablyan isocyanate-reactive tertiary amine polyether (c)(i) (in thequantities listed immediately above) but the preferred optional secondcomponent is an ammonium salt derivative of a fatty amido-amine (c)(iii)(preferably 3 to 24 percent by weight, more preferably 3 to 19 percentby weight, and most preferably 3 to 14 percent by weight). Althoughchain extenders and crosslinkers containing thiol groups can be used,chain extenders and crosslinkers containing hydroxyl or amino groups arepreferred. Preferred flame retardants include ammonium polyphosphate,alumina trihydrate, melamine, ANTIBLAZE NR-25, and halogen-containingcompounds. Preferred catalysts include tin compounds and tertiaryamines. Additives, if used at all, preferably include 0 to 3 percent byweight of a blowing agent, 0 to 2.5 percent by weight of an acidscavenger, 0 to 10 percent by weight of an internal mold release agent,0 to 3 percent by weight of a surfactant, 0 to 1 percent by weight of adefoaming agent, and 0 to 5 percent by weight of a water scavenger.

For urethane-based spray applications, preferred isocyanate-reactivecompositions of the invention contain 10 to 75 percent by weight (morepreferably 15 to 65 percent by weight) of isocyanate-reactive component(a); 1 to 50 percent by weight (more preferably 1.5 to 35 percent byweight) of chain extender or crosslinker (b); 5 to 15 percent by weight(more preferably 6 to 10 percent by weight) of component (c) ; 5 to 55percent by weight {more preferably 20 to 48 percent by weight) of flameretardant (d); and 0.01 to 1.5 percent by weight (more preferably 0.1 to1.0 percent by weight) of catalyst (e), all amounts being based on thetotal amount of components (a), (b), (c), (d), and (e). Catalyst (e) istypically added after all of the other components have been blended.Although chain extenders and crosslinkers containing thiol groups can beused, chain extenders and crosslinkers containing amino or hydroxylgroups are preferred. Component (c) is preferably 6 to 10 percent byweight of an isocyanate-reactive tertiary amine polyether (c)(i).Preferred flame retardants include phosphorus-, zinc-, aluminum-, andmagnesium-based compounds and halogen-containing compounds. Preferredcatalysts include tin(IV)-, bismuth-, and zinc-based compounds.Additives, if used at all, preferably include 0 to 2.5 percent by weightof an acid scavenger (preferably carbodiimides), 0 to 6 percent byweight of an internal mold release agent (preferably ester-based moldrelease agents), 0.01 to 1.0 percent by weight of a defoaming agent(preferably polyosiloxanes), and 1.0 to 10 percent by weight of a waterscavenger (preferably aluminosil icates).

The following examples further illustrate details for the preparationand use of the tompositions of this invention. The invention, which isset forth in the foregoing disclosure, is not to be limited either inspirit or scope by these examples. Those skilled in the art will readilyunderstand that known variations of the conditions and processes of thefollowing preparative procedures can be used to prepare thesecompositions. Unless otherwise noted, all temperatures are degreesCelsius and all parts and percentages are parts by weight and.percentages by weight, respectively.

EXAMPLES

The following starting materials were used to prepare theisocyanate-reactive compositions of the Examples:

Polyols and Polyamines

(a1) Polyether prepared by sequential reaction of glycerol and propyleneglycol (90:10 by weight) with propylene oxide (30%), a mixture ofethylene glycol (10%) and propylene glycol (40%), and capped withpropylene glycol (20%) having a hydroxyl number of 56

(a2) Glycerol-started polyether of propylene oxide and ethylene oxide(83 wt. % propylene oxide and 17 wt. % ethylene oxide) having a hydroxylnumber of 28

(a3) Polyester of neopentyl glycol and adipic acid having a hydroxylnumber of 112 (available as FORMREZ 55-112 from Witco Corporation)

(a4) Polyester of neopentyl glycol and adipic acid having a hydroxylnumber of 225 (available as FORMREZ 55-225 from Witco Corporation)

(a5) Aliphatically bound amine-terminated polyoxypropylene having afunctionality of 2 and a molecular weight about 2000 (available asJEFFAMINE D-2000 from Texaco Chemical Company)

(a6) Aliphatically bound amine-terminated polyoxypropylene having afunctionality of 3 and a molecular weight about 5000 (available asTEXRIM TR-5050 from Texaco Chemical Company)

(a7) Aminocrotonate-terminated polyether having a functionality of 4 anda molecular weight of about 4700 prepared from as described in U.S. Pat.Nos. 5,066,824 and 5,151,470 from (i) a difunctional polyether having ahydroxyl number of 56 prepared by the reaction of propylene glycol withpropylene oxide and (ii) 2-methyl-l,5-diaminopentane

(a8) Glycerol-started polyether of propylene oxide and ethylene oxide(87 wt. % propylene oxide and 13 wt. % ethylene oxide) having a primaryOH content of about 82% and a hydroxyl number of 28

(a9) Trimethylolpropane-started polyether of propylene oxide having ahydroxyl number of 370

(a10) Glycerol-started polyether of propylene oxide having a hydroxylnumber of 250

(a11) Polyether prepared by the reaction of sucrose, propylene glycol,and water (44:52:4 by weight) with propylene oxide having a hydroxylnumber of 380

Chain Extenders and Crosslinkers

(b1) Glycerol-started polyether of propylene oxide having afunctionality of 3 and a hydroxyl number of 1050 (molecular weight about160)

(b2) Mixture of 1-methyl-3,5-diethyl-2,4-diaminobenzene and1-methyl-3,5-diethyl-2,6-diaminobenzene (65:35 weight ratio)

(b3) Glycerol-started polyether of propylene oxide having a hydroxylnumber of 470

(b4) meta-Xylene diamine

Tertiary Amine and Ammonium Compounds

(c1) Ethylenediamine-started polyether of propylene oxide having afunctionality of 4 and a hydroxyl number of 630

(c2) Cocamidopropyldimethylamine (available as ADOGEN K-14 from WitcoCorporation)

(c3) Protonated ammonium salt of tall oil fatty acids and the amide oftall oil fatty acids and 3-(dimethylamino)propylamine (see U.S. Pat. No.3,726,952)

Flame Retardants

(d1) Diethyl N,N-bis(2-hydroxyethyl )aminomethylphosphonate (availableas FYROL 6 from Akzo Chemicals Inc.)

(d2) Dimethyl methylphosphonate (available as FYROL DMMP from AkzoChemicals Inc. )

(d3) Neutral cyclic phosphonate ester containing 21% phosphorus(available as ANTIBLAZE NR-25 from Albright and Wilson Americas, Inc.)

(d4) Oligomeric phosphate ester available as FYROL 51 from AkzoChemicals Inc.

(d5) Halogenated phosphate ester containing 6-8% phosphorus and 35-37%bromine available as FIREMASTER 836 from Great Lakes ChemicalCorporation

(d6) Alumina trihydrate

Catalysts

(e1) N,N-dimethylcyclohexylamine (available as POLYCAT 8 from AirProducts & Chemicals, Inc.)

(e2) Glycol acid salt of tetraethylenediamine and 1,1-dibutyltindiacetate (available as DABCO DC-2 from Air Products & Chemicals, Inc. )

(e3) Dibutyltin bis(isooctylmaleate) available as DABCO 125 from AirProducts & Chemicals, Inc.

(e4) Organotin carboxylate catalyst available as FOMREZ UL-28 from WitcoCorporation

(e5) Dimethyl tin mercaptide (available as FOMREZ UL-22 from WitcoCorporation)

(e6) Dibutyltin bis(dodecylmercaptide) (available as DABCO 120 from AirProducts & Chemicals, Inc.)

(e7) Bismuth neodecanoate available from Cosan Chemical Corporation

Additives

(f1) Silicone surfactant available as Dow Corning 193 from Dow CorningCorporation

(f2) Polyalkylene oxide/methylsiloxane copolymer surfactant available asY10809 from Union Carbide Chemicals and Plastics Co., Inc.

(f3) Ethoxylated fatty amines (mildly cationic surfactant available asTRYMEEN 6606 from Henkel Corporation)

(f4) Ethoxylated fatty amines (mildly cationic surfactant available asTRYMEEN 6617 from Henkel Corporation)

(f5) Silicone internal mold release available as Dow Corning 1248 fluidfrom Dow Corning Corporation

(f6) N,N,N'-(2-hydroxyethyl )-N'-tallow-1,3-propanediamine internal moldrelease having a hydroxyl number of 317 (available as ETHODUOMEEN T/13from Akzo Chemicals Inc.)

(f7) Amidine salt internal mold release prepared by the reaction of 12parts by weight of 2-(1-heptadecyl)-3-(2-hydroxyethyl)-2-imidazoline and88 parts by weight of a carboxy-functional silicone available as Q2-7119from Dow Corning Corporation) (e.g., U.S. Pat. No. 4,764,540)

(f8) 2-Hydroxypropanoic acid (blowing agent available from SterlingChemicals Inc. )

(f9) 2,2',6,6'-Tetraisopropyldiphenylcarbodiimide (acid scavengeravailable as STABOXAL I from Rhein Chemie Corp.)

(f10) 3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (acidscavenger available as ERL-4221 from Union Carbide)

(f11) Trimethyl orthoformate (acid scavenger)

(f12) Alkali aluminosilicate in castor oil (water scavenger availablefrom A. B. Colby or Bayer AG, Germany)

(f13) Alkali aluminosilicate (water scavenger available as BAYLITH Lfrom Bayer AG, Germany)

(f14) Defoamer concentrate containing dimethyl polysiloxane dispersed insilicic acid available as Tego FOAMEX N from Tego Chemie Service USA

The following organic isocyanates were used to prepare polyurethanesfrom the isocyanate-reactive compositions of the Examples:

(I) Mixture of equal parts by weight of (i) a liquid semi-prepolymer(NCO content about 23%) prepared by the reaction of 4,4'-diphenylmethanediisocyanate and tripropylene glycol in a molar ratio of about 5:1 and(ii) an aniline-formaldehyde condensation product (NCO content about 2%;average functionality about 2.8) containing about 44% monomeric4,4'-diphenylmethane diisocyanate (the balance being essentially higherfunctional ity homologs)

(II) Polyisocyanate containing about 60% monomeric diphenylmethanediisocyanate and 40% polyphenyl-polymethylenepolyisocyanate and havingan NCO content about 33% and a viscosity (25° C.) of 50-100 cps

(III) Isocyanate prepolymer having an NCO content of 27% (prepared froman organic polyisocyanate and a substoichiometric amount of a polyetherpolyol) available as BAYTEC RE527A from Miles Inc.

The following flame retardants were blended with the isocyanatecomponents for use in spray systems:

(d7) Aromatic brominated flame retardant available as SAYTEX 8010 fromEthyl Corporation

(d8) Pentabromodiphenyl oxide (available as DE-71 from Great LakesChemical Corporation)

Examples 1-25 Microcellular Rigid Integral Skin Foam Systems

Isocyanate-reactive blends were prepared in approximately four-literquantities by adding the components in decreasing volume order (withcatalysts normally being added last). For purposes of carrying outcomparison experiments, each set of examples was carried out byinitially preparing a master batch containing all ingredients havingconstant amounts and then adding only the variable components to formthe blends.

After the isocyanate-reactive blends were prepared and allowed to standfor specified periods of time, the blends were mixed with organicpolyisocyanates at an isocyanate index of 110 (i.e., 10% excess NCO),indicated in the following Tables as parts by weight of polyisocyanateper 100 parts by weight of the NCO-reactive blends. Stabilities of thevarious blends were determined by observing the gel times for theisocyanate addition reactions.

The isocyanate-reacttve blends and the organic polyisocyanates wereseparately brought to a temperature of 25° C. before being mixed. Thereaction mixtures were mixed in a high speed mixer for about 6-8 secondsand poured into a cup. A timer was started when mixing was begun. Geltimes were determined by observing the time at which the first thinstring of polyurethane could be pulled by plunging an applicator stickin and out of the mixture. Gel time determinations were reproduciblewithin about 1.5 seconds.

The reaction procedure and gel time determinations were carried outimmediately upon preparing the isocyanate-reactive blends (i.e., nostorage) and after storage at room temperature for one day, four days,one week, two weeks, three weeks, four weeks, two months, three months,and six months. In general, tests were carried out until relativelylarge changes were evident or until no further deterioration could beobserved. Smaller changes in reaction time indicate improved stabilityof the NCO-reactive blends.

Where indicated, the following Examples apply an experimental designmethod known as the "Taguchi Experimental Design Approach" for productoptimization by analysis of variance. See Y. Wu and W. H. Moore, QualityEngineerinq Product and Process Design Optimization (American DesignInstitute, Inc. 1985). The Taguchi method allows the simultaneousexamination of several variables having differing relative amounts andtypes. Where used in the following Examples, the experiments are listedorthogonally in the Tables so that the effects obtained by varying agiven parameter can be visually separated from other varying effects.

Examples 1-8

Each of Examples 1-8 includes a base blend 1 containing the followingcomponents (parts by weight):

    ______________________________________                                        Polyether (a1)          20 parts                                              Polyester (a4)          20 parts                                              Crosslinker (b1)        50 parts                                              Flame retardant (d1)    20 parts                                              Surfactant (f1)          3 parts                                              Mold release (f5)        1 part                                               Mold release (f6)        5 parts                                              Mold release (f7)      3.5 parts                                              Blowing agent (f8)     1.5 parts                                              ______________________________________                                    

Quantities of the remaining components and test results for Examples 1-8are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Compositions and results for Examples 1-8.                                    Components                                                                    (parts by                                                                              Examples                                                             weight)  1      2      3    4    5    6    7    8                             ______________________________________                                        NCO-reac-                                                                     tive blend.sup.(1)                                                            Ammonium --     --     6    6    --   --   6    6                             salt (c3)                                                                     Flame    20     20     20   20   --   --   --   --                            retardant (d2)                                                                Flame    --     --     --   --   20   20   20   20                            retardant (d4)                                                                Catalyst (e1)                                                                          3.5    2.5    2.5  3.5  3.5  2.5  2.5  3.5                           Catalyst (e5)                                                                          0.4    0.2    0.4  0.2  0.4  0.2  0.4  0.2                           Acid     2      --     --   2    --   2    2    --                            scavenger (f9)                                                                Water    2      --     2    --   --   2    --   2                             scavenger (f12)                                                               Water    --     --     0.2  0.2  0.2  0.2  --   --                            Isocyanate                                                                    component                                                                     Polyiso- 141    146    141  141  147  149  144  143                           cyanate (I).sup.(2)                                                           Isocyanate                                                                             110    110    110  110  110  110  110  110                           index                                                                         Change in gel                                                                 time (sec).sup.(3)                                                            Three weeks                                                                            10     10     5    6    26   24   15   26                            Two months                                                                             13     16     7    8    --   --   --   --                            ______________________________________                                         .sup.(1) Isocyanatereactive blends also include base blend 1 (described       above).                                                                       .sup.(2) Parts by weight of polyisocyanate (I) per 100 parts by weight of     the NCOreactive blend.                                                        .sup.(3) Change in gel time relative to reaction after no storage of          NCOreactive blend.                                                       

Examples 1-8 were performed in accordance with the Taguchi method. Thevariable and corresponding levels (listed in increasing numeric orderwhere appropriate) were as follows: ammonium salt (c3) at 0 and 6 partsby weight; flame retardants (d2) and (d4); catalyst (e1) at 2.5 and 3.5parts by weight; catalyst (e5) at 0.2 and 0.4 parts by weight; acidscavenger (f9) at 0 and 2 parts by weight; water scavenger (f12) at 0and 2 parts by weight; and water at 0 and 0.2 parts by weight. Variancetable analysis for the compositions shown in Table 1 (above) after fourweeks storage are as follows:

    ______________________________________                                        Level               Level sums* Percent                                       Variable                                                                             #1       #2     #1     #2    contribution**                            ______________________________________                                        (c3)   0        6      174    128   11.3                                      (d2)/(d4)                                                                            (d2)     (d4)    92    210   74.6                                      (e1)   2.5      3.5    139    163   3.0                                       (e5)   0.2      0.4    163    139   3.0                                       (fg)   0        2      169    133   6.9                                       (f12)  0        2      151    151   --                                        Water  0        0.2    154    148   0.1                                       Error                               1.1                                       ______________________________________                                         *Level sums are derived in the Taguchi analysis for each variable at          levels #1 and #2. The smaller of the level sum numbers for each variable      indicates the more positive effect on shelf life.                             **Percent contribution (rho) compares the percent contribution of each        source of variation to the total.                                        

The Taguchi analysis shows that although the type of flame retardant hasthe greatest effect on shelf-life stability in these Examples, theaddition of polyether amine (c3) significantly improves shelf liferegardless of which flame retardant is used. In addition, thestabilizing effect of polyether amine (c3) is greater than the effectobtained by adding acid scavengers or water scavengers, which are knownto help improve shelf-life stability, for example, when using acidicflame retardants. The analysis shows that catalyst type and amount arealso significant but are less significant than the effect of usingpolyether amine (c3).

Examples 9-17

Each of Examples 9-17 includes a base blend 3 containing the followingcomponents (parts by weight):

    ______________________________________                                        Polyether (a2)         40 parts                                               Crosslinker (b1)       53 parts                                               Flame retardant (d2)   23 parts                                               Catalyst (e1)         2.5 parts                                               Surfactant (f1)         3 parts                                               Mold release (f5)       1 part                                                Mold release (f6)       5 parts                                               Mold release (f7)     3.5 parts                                               Blowing agent (f8)    1.5 parts                                               ______________________________________                                    

Quantities of the remaining components and test results for Examples9-17 are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________    Compositions and results for Examples 9-17.                                   Components   Examples                                                         (parts by weight)                                                                          9  10 11 12 13 14 15 16 17                                       __________________________________________________________________________    NCO-reactive blend.sup.(1)                                                    Chain extender (b2)                                                                        3  3  3  -- -- -- -- -- --                                       Amine polyether (c1)                                                                       -- -- -- -- -- -- 10 10 10                                       Ammonium salt (c3)                                                                         3  6  9  3  6  9  3  6  9                                        Catalyst (e3)                                                                              -- 0.8                                                                              -- -- -- 0.8                                                                              0.8                                                                              -- --                                       Catalyst (e4)                                                                              0.2                                                                              -- -- -- 0.2                                                                              -- -- -- 0.2                                      Catalyst (e5)                                                                              -- -- 0.2                                                                              0.2                                                                              -- -- -- 0.2                                                                              --                                       Acid scavenger (f9)                                                                        -- 2  -- 2  -- -- -- -- 2                                        Acid scavenger (f10)                                                                       0.002                                                                            -- -- -- -- 0.002                                                                            -- 0.002                                                                            --                                       Isocyanate component                                                          Polyisocyanate (I).sup.(2)                                                                 131                                                                              131                                                                              133                                                                              137                                                                              133                                                                              129                                                                              136                                                                              137                                                                              132                                      Isocyanate index                                                                           110                                                                              110                                                                              110                                                                              110                                                                              110                                                                              110                                                                              110                                                                              110                                                                              110                                      Change in gel time (sec).sup.(3)                                              Two weeks    8  2  7  7  5  11 2  3  2                                        Six months   7  -- 19 21 -- 11 3  6  0                                        __________________________________________________________________________     .sup.(1) Isocyanatereactive blends also include base blend 2 (described       above).                                                                       .sup.(2) Parts by weight of polyisocyanate (I) per 100 parts by weight of     the NCOreactive blend.                                                        .sup.(3) Change in gel time relative to reaction after no storage of          NCOreactive blend.                                                       

Examples 9-17 were also performed in accordance with the Taguchi method.The variable and corresponding levels (listed in increasing numericorder where appropriate) were as follows: amine type using none,extender (b2), and amine polyether (c1); ammonium salt (c3) at 3, 6, and9 parts by weight; catalyst type using catalysts (e5), (e4), and (e3);and acid scavenger type using acid scavengers (f9) and (f10) and none.(Catalyst amounts were adjusted so that the reactivity profile wasidentical on day zero for all Examples. Acid scavenger levels wereselected for known optimum effect.) Variance table analysis for thecompositions shown in Table 2 (above) after two weeks storage are asfollows:

    ______________________________________                                                                        Percent                                              Level       Level sums*  contri-                                       Variable #1     #2     #3    #1   #2   #3   bution**                          ______________________________________                                        Amine type                                                                             0      (b2)   (c1)  47   33   11   56.7                              (c3)     3      6      9     33   22   36   9.2                               Catalyst type                                                                          (e5)   (e4)   (e3)  35   26   30   3.3                               Acid     (f9)   (f10)  None  18   44   29   29.2                              scavenger                                                                     type                                                                          Error                                       1.5                               ______________________________________                                         *Level sums are derived in the Taguchi analysis for each variable at          levels #1, #2, and #3. The smaller of the level sum numbers for each          variable indicates the more positive effect on shelf life.                    **Percent contribution (rho) compares the percent contribution of each        source of variation to the total.                                        

The Taguchi analysis shows that base polyether levels and amine type(including amine polyether (c1)) have the greatest effect on shelf-lifestability in these Examples. However, the addition of ammonium salt (c3)also significantly improves shelf life. The analysis also shows thatcatalyst type and acid scavenger type have relatively little effect onshelf-life stability.

Examples 18-19

Examples 18 and 19 used essentially the same components as Examples15-17 except for the addition of flame retardant (d3). Quantities ofcomponents and test results for Examples 10 and 11 are shown in Table 3.

Example 18 shows that the use of amine polyether (c1) along with anoptimal amount of ammonium salt (c3) provides no change in shelf-lifestability after three weeks or even three months, regardless of the typeof catalyst used or whether an acid scavenger is present. Example 19shows that this same effect is obtained when using an alternative flameretardant (d2) in combination with flame retardant (d3) (at comparativecombustion modifying performance levels).

                  TABLE 3                                                         ______________________________________                                        Compositions and results for Examples 18 and 19.                              Components          Examples                                                  (parts by weight)   18      19                                                ______________________________________                                        NCO-reactive blend                                                            Polyether (a2)      32      32                                                Crosslinker (b1)    58      58                                                Amine polyether (c1)                                                                              10      10                                                Ammonium salt (c3)  6       6                                                 Flame retardant (d2)                                                                              --      10.5                                              Flame retardant (d3)                                                                              21      10.5                                              Catalyst (e1)       2       2                                                 Catalyst (e3)       0.4     0.4                                               Surfactant (f1)     3       3                                                 Mold release (f5)   1       1                                                 Mold release (f6)   5       5                                                 Mold release (f7)   3.5     3.5                                               Blowing agent (f8)  1.3     1.3                                               Isocyanate component                                                          Polyisocyanate (I).sup.(1)                                                                        152     151                                               Isocyanate index    110     110                                               Change in gel time (sec).sup.(2)                                              Three weeks         3       3                                                 Three months        4       2                                                 ______________________________________                                         .sup.(1) Parts by weight of polyisocyanate (I) per 100 parts by weight of     the NCOreactive blend.                                                        .sup.(2) Change in gel time relative to reaction after no storage of          NCOreactive blend.                                                       

Examples 20-21

Examples 20 and 21 were carried out using the same components andquantities except that Example 20 contained no flame retardant componentand Example 21 contained flame retardants (d2) and (d3). Quantities ofcomponents and test results for Examples 20 and 21 are shown in Table 4.

Examples 20 and 21 show that amine components (c1) and (c3) provideisocyanate-reactive blends having storage stability as good ascompositions having no phosphorus-containing flame retardant.

                  TABLE 4                                                         ______________________________________                                        Compositions and results for Examples 20-21.                                  Components          Examples                                                  (parts by weight)   20      21                                                ______________________________________                                        NCO-reactive blend                                                            Polyether (a2)      32      32                                                Crosslinker (b1)    58      58                                                Amine polyether (c1)                                                                              10      10                                                Ammonium salt (c3)  6       6                                                 Flame retardant (d2)                                                                              --      11                                                Flame retardant (d3)                                                                              --      11                                                Catalyst (e2)       0.8     0.8                                               Catalyst (e3)       0.4     0.4                                               Surfactant (f2)     3       3                                                 Mold release (f6)   5       5                                                 Mold release (f7)   3.5     3.5                                               Blowing agent (f8)  1.3     1.3                                               Isocyanate component                                                          Polyisocyanate (I).sup.(1)                                                                        187     155                                               Isocyanate index    110     110                                               Change in gel time (sec).sup.(2)                                                                  0       0                                                 Three weeks                                                                   ______________________________________                                         .sup.(1) Parts by weight of polyisocyanate (I) per 100 parts by weight of     the NCOreactive blend.                                                        .sup.(2) Change in gel time relative to reaction after no storage of          NCOreactive blend.                                                       

Examples 22-25

Examples 23 and 25 compare the effect of using amine polyether (c1) incombination with different flame retardants. Examples 22 and 24 are therespective comparison examples containing no amine polyether (c1).Quantities of components and test results for Examples 22-25 are shownin Table 5.

Amine polyether (c1) provides improved stabilization of foam systemscontaining alternative flame retardants, even when ammonium salt (c3) isalso present.

                  TABLE 5                                                         ______________________________________                                        Compositions and results for Examples 22-25.                                  Components      Examples                                                      (parts by weight)                                                                             22      23       24    25                                     ______________________________________                                        NCO-reactive blend                                                            Polyether (a2)  40      40       40    40                                     Crosslinker (b1)                                                                              53      53       53    53                                     Amine polyether (c1)                                                                          --      10       --    10                                     Ammonium salt (c3)                                                                            6       6        6     6                                      Flame retardant (d4)                                                                          20      20       --    --                                     Flame retardant (d5)                                                                          --      --       20    20                                     Catalyst (e1)   2       2        2     2                                      Catalyst (e3)   0.4     0.4      0.4   0.4                                    Surfactant (f1) 3       3        3     3                                      Mold release (f5)                                                                             1       1        1     1                                      Mold release (f6)                                                                             5       5        5     5                                      Mold release (f7)                                                                             3.5     3.5      3.5   3.5                                    Blowing agent (f8)                                                                            1.3     1.3      1.3   1.3                                    Isocyanate component                                                          Polyisocyanate (I).sup.(1)                                                                    140     139      135   139                                    Isocyanate index                                                                              110     110      110   110                                    Change in gel time sec .sup.(2)                                                               21      11       9     3                                      Three weeks                                                                   ______________________________________                                         .sup.(1) Parts by weight of polyisocyanate (I) per 100 parts by weight of     the NCOreactive blend.                                                        .sup.(2) Change in gel time relative to reaction after no storage of          NCOreactive blend.                                                       

Examples 26-43 Rigid Non-Microcellular Foam Systems

Isocyanate-reactive blends used for the preparation of rigidnon-microcellular applications were prepared as described for Examples1-25. Because the isocyanate addition reaction is relatively rapid formost of these examples, the reaction was retarded by adding 25 parts byweight of MESAMOLL alkylsulfonic acid ester of phenol to theisocyanate-reactive blend, with appropriate adjustments in quantitiesbeing made to obtain the desired isocyanate index. Comparisons of thereactivities for each isocyanate-reactive blend showed that the additionof MESAMOLL did not significantly affect the aging process.

Examples 26-31

Examples 26-31 illustrate the stabilizing effect of amine polyether (c1)in rigid non-microcellular systems containing flame retardants. Example26 is a comparison example containing no phosphorus flame retardant.Quantities of components and test results for Examples 26-31 are shownin Table 6.

Examples 27 and 28 show comparable changes in reactivity when usingeither of the flame retardants (d2) or (d3) in the absence of aminepolyether (c1). Examples 29 and 30 show that reactivity of the blends islost over a two-month period when using catalyst (e1), either alone oras a mixture with catalyst (e6), in the absence of amine polyether (c1).

Examples 26-30 did not require the use of the MESAMOLL alkylsulfonicester because the reactivities of the respective isocyanate-reactiveblends decreased so rapidly that the isocyanate addition reaction wereeasily compared without being retarded. Example 31 (as well assubsequent Examples 32-43) were carried out in the presence of theMESAMOLL alkylsulfonic ester. The data show that even with the additionof MESAMOLL alkylsulfonic ester in Example 31 to slow the reaction, thechange in reactivity was not dramatically affected even after sixmonths, a result that compares favorably to those systems not containingany flame retardant (such as Example 26).

                  TABLE 6                                                         ______________________________________                                        Compositions and results for Examples 26-31.                                  Components     Examples                                                       (parts by weight)                                                                            26     27     28   29   30   31                                ______________________________________                                        NCO-reactive blend                                                            Polyester (a3) --     --     --   15   15   --                                Polyester (a4) 15     15     15   --   --   15                                Polyether (a5) --     --     --   35   35   --                                Polyether (a6) 25     25     25   --   --   25                                Crosslinker (b1)                                                                             60     60     60   50   50   60                                Amine polyether (c1)                                                                         --     --     --   --   --   10                                Flame retardant (d2)                                                                         --     20     --   --   --   20                                Flame retardant (d3)                                                                         --     --     21   21   21   --                                Catalyst (e1)  5      5      5    5    1    1.5                               Catalyst (e6)  --     --     --   --   0.65 0.4                               Surfactant (f1)                                                                              3      3      3    3    3    3                                 Mold release (f5)                                                                            1      1      1    1    1    1                                 Mold release (f7)                                                                            3.5    3.5    3.5  3.5  3.5  3.5                               Isocyanate component                                                          Polyisocyanate (II).sup.(1)                                                                  153    130    129  107  111  114                               Isocyanate index                                                                             110    110    110  110  110  110                               Change in gel time (sec).sup.(2)                                              Three weeks    --     30     23   3    45   7                                 Six months     5      --     --   48   --   14                                ______________________________________                                         .sup.(1) Parts by weight of polyisocyanate (II) per 100 parts by weight o     the NCOreactive blend.                                                        .sup.(2) Change in gel time relative to reaction after no storage of          NCOreactive blend.                                                       

Examples 32-40

Each of Examples 32-40 includes a base blend 4 containing the followingcomponents (parts by weight):

    ______________________________________                                        Polyester (a4)          15 parts                                              Polyether (a6)          25 parts                                              Crosslinker (b1)        60 parts                                              Flame retardant (d2)    20 parts                                              Catalyst (e1)          1.5 parts                                              Surfactant (f1)          3 parts                                              Mold release (f5)        1 part                                               Mold release (f7)      3.5 parts                                              ______________________________________                                    

Quantities of the remaining components and test results for Examples32-40 are shown in Table 7.

                                      TABLE 7                                     __________________________________________________________________________    Compositions and results for Examples 32-40.                                  Components   Examples                                                         (parts by weight)                                                                          32 33 34 35 36 37 38 39 40                                       __________________________________________________________________________    NCO-reactive blend.sup.(1)                                                    Chain extender (b2)                                                                        3  3  3  -- -- -- -- -- --                                       Amine polyether (c1)                                                                       -- -- -- -- -- -- 10 10 10                                       Catalyst (e4)                                                                              -- 0.2                                                                              -- -- -- 0.2                                                                              -- -- 0.2                                      Catalyst (e5)                                                                              0.2                                                                              -- -- 0.2                                                                              -- -- 0.2                                                                              -- --                                       Catalyst (e6)                                                                              -- -- 0.4                                                                              -- 0.4                                                                              -- -- 0.4                                                                              --                                       Surfactant (f3)                                                                            6  -- -- -- 6  -- -- -- 6                                        Surfactant (f4)                                                                            -- -- 6  -- -- 6  6  -- --                                       Acid scavenger (f9)                                                                        -- -- 2  2  -- -- -- -- 2                                        Acid scavenger (f11)                                                                       -- 0.002                                                                            -- -- 0.002                                                                            -- 0.002                                                                            -- --                                       Isocyanate component                                                          Polyisocyanate (II).sup.(2)                                                                109                                                                              112                                                                              108                                                                              110                                                                              108                                                                              108                                                                              111                                                                              114                                                                              110                                      Isocyanate index                                                                           110                                                                              110                                                                              110                                                                              110                                                                              110                                                                              110                                                                              110                                                                              110                                                                              110                                      Change in gel time (sec).sup.(3)                                              One week     31 33 10 17 14 62 4  2  10                                       Six months   -- -- -- -- -- -- 23 14 --                                       __________________________________________________________________________     .sup.(1) Isocyanatereactive blends also include base blend 4 (described       above).                                                                       .sup.(2) Parts by weight of polyisocyanate (II) per 100 parts by weight o     the NCOreactive blend.                                                        .sup.(3) Change in gel time relative to reaction after no storage of          NCOreactive blend.                                                       

Examples 32-40 were performed in accordance with the Taguchi method. Thevariable and corresponding levels (listed in increasing numeric orderwhere appropriate) were as follows: amine type using none, extender(b2), and amine polyether (c1); surfactant type using none andsurfactants (f4) and (f3); catalyst type using catalysts (e5), (e4), and(e6); and acid scavenger type using acid scavengers (f9) and (f10) andnone. (Catalyst amounts were adjusted so that the reactivity profile wasidentical on day zero for all Examples. Acid scavenger levels wereselected for known optimum effect.) Variance table analysis for thecompositions shown in Table 7 (above) after one week storage are asfollows:

    __________________________________________________________________________              Level      Level sums*                                                                             Percent                                        Variable  #1  #2 #3  #1 #2  #3 contribution**                                 __________________________________________________________________________    Amine type                                                                              None                                                                              (b2)                                                                             (c1)                                                                              186                                                                              153  35                                                                              37.1                                           Surfactant type                                                                         None                                                                              (f4)                                                                             (f3)                                                                              105                                                                              154 115                                                                              3.9                                            Catalyst type                                                                           (e5)                                                                              (e4)                                                                             (e6)                                                                              109                                                                              211  54                                                                              37.4                                           Acid scavenger type                                                                     (f9)                                                                              (f10)                                                                            None                                                                               76                                                                              106 192                                                                              21.4                                           Error                          0.3                                            __________________________________________________________________________     *Level sums are derived in the Taguchi analysis for each variable at          levels #1, #2, and #3. The smaller of the level sum numbers for each          variable indicates the more positive effect on shelf life.                    **Percent contribution (rho) compares the percent contribution of each        source of variation to the total.                                        

The Taguchi analysis shows that amine type (including amine polyether(c1)) and catalyst type have the greatest effect on shelf-life stabilityin these Examples. Although, as expected, acid scavenger type has asignificant effect on shelf-life stability, the effect is not as greatas with polyether amine (c1). The analysis also shows that surfactanttype has relatively little effect on shelf-life stability.

Example 41

Example 31 was repeated except for adding tertiary amine (c2).Quantities of components are shown in Table 8.

The change in gel time after six months (relative to a reaction carriedout after no storage of the NCO-reactive blend) was 7 sec. That is,tertiary amine (c2) provides additional stabilization to blendscontaining amine polyether (c1) comparable to the stability of a blendcontaining no flame retardants (e.g., Example 26).

                  TABLE 8                                                         ______________________________________                                        Composition for Example 41.                                                                    Quantities                                                   Components       (parts by weight)                                            ______________________________________                                        NCO-reactive blend                                                            Polyester (a4)   15                                                           Polyether (a6)   25                                                           Crosslinker (b1) 60                                                           Amine polyether (c1)                                                                           10                                                           Tertiary amine (c2)                                                                            6                                                            Flame retardant (d2)                                                                           20                                                           Catalyst (e1)    1.5                                                          Catalyst (e6)    0.4                                                          Surfactant (f1)  3                                                            Mold releasd (f5)                                                                              1                                                            Mold release (f7)                                                                              3.5                                                          Isocyanate component                                                          Polyisocyanate (II).sup.(1)                                                                    112                                                          Isocyanate index 110                                                          ______________________________________                                         .sup.(1) Parts by weight of polyisocyanate (II) per 100 parts by weight o     the NCOreactive blend.                                                   

Examples 42-43

Example 43 illustrates a dramatic stabilizing effect of amine polyether(c1) on a rigid non-microcellular system based on an alternativeamine-terminated polyether (a7) containing flame retardants. Example 42is a comparison example containing no amine component (c1). Quantitiesof components and test results for Examples 42 and 43 are shown in Table9.

                  TABLE 9                                                         ______________________________________                                        Compositions and results for Examples 42-43.                                  Components          Examples                                                  (parts by weight)   42      43                                                ______________________________________                                        NCO-reactive blend                                                            Polyester (a4)      15      15                                                Polyether (a7)      25      25                                                Crosslinker (b1)    60      60                                                Amine polyether (c1)                                                                              --      10                                                Flame retardant (d2)                                                                              11      11                                                Flame retardant (d3)                                                                              11      11                                                Catalyst (e1)       1.5     1.5                                               Catalyst (e6)       0.4     0.4                                               Surfactant (f2)     3       3                                                 Mold release (f5)   1       1                                                 Hold release (f7)   3.5     3.5                                               Isocyanate component                                                          Polyisocyanate (II).sup.(1)                                                                       110     113                                               Isocyanate index    110     110                                               Change in gel time (sec).sup.(2)                                                                  80      3                                                 One week                                                                      ______________________________________                                         .sup.(1) Parts by weight of polyisocyanate (II) per 100 parts by weight o     the NCOreactive blend.                                                        .sup.(2) Change in gel time relative to reaction after no storage of          NCOreactive blend.                                                       

Examples 44-54 Spray Systems

Isocyanate-reactive blends were prepared in a fifty-kilogram containerby adding the components in the sequence (a), (b), (c), (f), (d), andfinally (e) (with catalysts normally being added last). Theisocyanate-reactive blends were mixed for a total of 30 minutes (orabout 15 minutes after the last component was added). Isocyanateprepolymer blends were prepared by adding flame retardant (d7) or (d8)to the isocyanate prepolymer. The isocyanate prepolymer blends weremixed for 30 minutes under a nitrogen atmosphere. Theisocyanate-reactive blends were allowed to stand for a minimum of twelvehours after being mixed and were then mixed with the isocyanateprepolymers at the isocyanate indexes shown in the Tables. Mixing wascarried out in a spray gun equipped with a static or impingement mixerusing spray equipment having a metering pump. Spraying was carried outat a temperature of 60° C. and a spray pressure of 10 MPa. The materialswere generally sprayed to a thickness of 3 to 4 mm onto a mirroredsurface or a polyethylene sheet from which the sprayed polyurethanecould release easily.

For laboratory gel time experiments, a fifty gram sample of theisocyanate-reactive blend was mixed with an isocyanate prepolymer blendat 25° C. in equal volumes or at a volumetric ratio of four parts of thetsocyanate-reactive blend for each three parts of the polyisocyanate.Mixing was carried out using Servodyne electronic mixer (Cole PalmerInstrument Company) equipped with a constant speed stirrer. Gel time wasdetermined by observing the time at which voltage across the stirrer(which is proportional to viscosity) crossed the 50 mV level (whichcorresponds to a viscosity of 13500 cps and to the time at which thepolyurethane starts to form gel strings when an applicator stick isplunged into and out of the mixture). Gel time results were reproducibleto within 7 to 12 seconds, depending on the amount of filler in thesystem.

Examples 44-49

Examples 44-49 were carried out in the absence of tertiary amine ofammonium compounds corresponding to component (c), both with and withoutflame retardants, for purposes of comparison. The reaction procedure andgel time determinations were carried out on the day after theisocyanate-reactive blends were prepared. When no signs of gelling wereobserved within 300 seconds, the blends were considered to havedeteriorated with complete loss of reactivity within 24 hours.Quantities of components and test results for Examples 44-49 are shownin Table 10.

                  TABLE 10                                                        ______________________________________                                        Compositions and results for Examples 44-49.                                  Components   Examples                                                         (parts by weight)                                                                          44     45     46   47    48   49                                 ______________________________________                                        NCO-reactive blend                                                            Polyether (a8)                                                                             6      6      6    6     6.0  4.8                                Polyether (a9)                                                                             86.6   86.6   --   --    --   --                                 Polyether (a10)                                                                            --     --     --   --    39   39                                 Polyether (a11)                                                                            --     --     86.6 86.6  --   --                                 Crosslinker (b3)                                                                           --     --     --   --    47.7 47.7                               Chain extender (b4)                                                                        2.3    2.3    2.3  2.3   2.3  2.3                                Flame retardant (d2)                                                                       --     --     --   13.1  --   13.1                               Flame retardant (d3)                                                                       --     --     --   13.1  --   13.1                               Flame retardant (d6)                                                                       --     68.3   --   --    --   --                                 Catalyst (e7)                                                                              0.23   0.23   0.23 0.23  0.23 0.23                               Water scavenger (f13)                                                                      5.75   5.75   5.75 5.75  5.75 5.75                               Defoamer (f14)                                                                             0.1    0.1    0.1  0.1   0.1  0.1                                Isocyanate component                                                          Prepolymer (III)                                                                           100    100    100  70    100  100                                Flame retardant (d10)                                                                      --     --     --   30    --   --                                 Isocyanate index                                                                           93     115    93   95    93   100                                Volume ratio.sup.(1)                                                                       3:4    3:4    3:4  3:4   3:4  3:4                                Gel data                                                                      Gel time (sec)                                                                             43     486    55   >300  54   >300                               Complete loss of                                                                           No     Yes    No   Yes   No   Yes                                reactivity?                                                                   ______________________________________                                         .sup.(1) Volume ratio is the volumetric ratio of the amount of the            isocyanate component to the amount of the NCOreactive blend.             

Examples 44 to 49 show that the presence of flame retardants (d2), (d3),(d6), and (d10) causes a complete loss in shelf-life stability.

Examples 50-54

Examples 51-54 were carried out in the presence of tertiary aminecomponent (c1) in the presence of various flame retardants. ComparativeExample 50 was carried out in the same manner as Example 51 except thatthe tertiary amine component (c1) was omitted. The reaction proceduresand gel time determinations were carried out on the day after theisocyanate-reactive blends were prepared and again after storage at23°-25° C. for two weeks and four or more weeks. Quantities ofcomponents and test results for Examples 50-54 are shown in Table 11.

                  TABLE 11                                                        ______________________________________                                        Compositions and results for Examples 50-54.                                  Components     Examples                                                       (parts by weight)                                                                            50      51     52    53   54                                   ______________________________________                                        NCO-reactive blend                                                            Polyether (a8) 3.3     3.3    3.5   4.2  4.2                                  Polyether (a10)                                                                              21.5    21.5   22.6  27.3 27.3                                 Crosslinker (b3)                                                                             26.2    26.2   27.7  33.4 33.4                                 Chain extender (b4)                                                                          1.3     1.3    1.3   1.6  1.6                                  Amine polyether (c1)                                                                         --      10     10    10   10                                   Flame retardant (d2)                                                                         --      --     10    10   10                                   Flame retardant (d3)                                                                         --      --     10    10   10                                   Flame retardant (d6)                                                                         45      45     12    --   --                                   Catalyst (e3)  0.06    0.06   0.05  0.05 --                                   Catalyst (e7)  0.13    0.13   0.14  0.17 0.17                                 Water scavenger (f13)                                                                        2.6     2.6    2.8   3.3  3.3                                  Defoamer (fl4) 0.06    0.06   0.06  0.07 0.07                                 Isocyanate component                                                          Prepolymer (III)                                                                             65      65     65    65   70                                   Flame retardant (d7)                                                                         35      35     35    35   30                                   Isocyanate index                                                                             105     98     105   110  110                                  Volume ratio.sup.(1)                                                                         3:4     3:4    1:1   1:1  1:1                                  Change in gel time (sec).sup.(2)                                              Two weeks      --      3      5     8    10                                   Four weeks     >120    8      7     10   --                                   ______________________________________                                         .sup.(1) Volume ratio is the volumetric ratio of the amount of the            isocyanate component to the amount of the NCOreactive blend.                  .sup.(2) Change in gel time relative to reaction after no storage of          NCOreactive blend.                                                       

Examples 50 to 54 show that amine polyether (c1) significantly improvesshelf-life stability.

Although the invention has been described in detail in the foregoing forthe purpose of illustration, it is to be understood that such detail issolely for that purpose and that variations can be made therein by thoseskilled in the art without departing from the spirit and scope of theinvention except as it may be limited by the claims.

What is claimed is:
 1. A polyurethane containing a flame retardantprepared by the isocyanate addition reaction, at an isocyanate index offrom 80 to 130 in the absence of a blowing agent, of an organicpolyisocyanate with a storage-stable isocyanate-reactive compositioncomprising(a) 10 to 90 percent by weight, based on the total ofcomponents (a), (b), (c), (d), and (e), of at least oneisocyanate-reactive compound having a molecular weight of 400 to 10,000and a functionality of 2 to 7; (b) 0.6 to 67 percent by weight, based onthe total of components (a), (b), (c), (d), and (e), of at least oneisocyanate-reactive compound having a molecular weight of less than 399and a functionality of 2 to 6; (c) 0.7 to 30 percent by weight, based onthe total of components (a), (b), (c), (d), and (e), of a tertiary amineor ammonium compound selected from the group consisting of(i) anisocyanate-reactive tertiary amine polyether having a molecular weightof from 100 to 1000 and having the formula

    R[NR.sup.1 R.sup.2 ].sub.m

wherein R is saturated or unsaturated C₂ -C₈ aliphatic or C₂ -C₈aliphatic substituted with --OH,--SH, or NHR^(a) wherein R^(a) is C₁ -C₈alkyl or C₂ -C₈ alkenyl; saturated or unsaturated C₅ -C₈ cycloaliphaticor C₅ -C₈ cycloaliphatic substituted with C₁ -C₈ alkyl, C₂ -C₈ alkenyl,C₁ -C₈ alkylene, --OH, --SH, or NHR^(a) wherein R^(a) is alkyl oralkenyl; or five- or six-membered aromatic or heteroaromatic optionallysubstituted with C₁ -C₈ alkyl, C₁ -C₈ alkoxy, halogen, cyano, nitro, C₁-C₈ alkylene, --OH, --SH, or NHR^(a) wherein R^(a) is C₁ -C₈ alkyl or C₂-C₈ alkenyl; R¹ and R² are independently polyether groups terminatedwith isocyanate-reactive groups selected from --OH, --SH, and NHR^(b)wherein R^(b) is C₁ -C₈ alkyl or C₂ -C₈ alkenyl; and m is an integer offrom 1 to 4; (ii) a fatty amido-amine; (iii) an ammonium salt derivativeof a fatty amido-amine; and (iv) mixtures thereof; (d) 5 to 55 percentby weight, based on the total of components (a), (b), (c), (d), and (e),of a flame retardant; (e) 0.007 to 6 percent by weight, based on thetotal of components (a), (b), (c), (d), and (e), of a catalyst selectedfrom tertiary amines, organic metal compounds, and mixtures thereof; and(f) 0 to 15 percent by weight, based on the total of components (a),(b), (c), (d), and ( e ), of additives.
 2. A polyurethane according toclaim 1 wherein isocyanate-reactive compound (a) has a functionality of2 to
 4. 3. A polyurethane according to claim 1 whereinisocyanate-reactive compound (b) has a functionality of 2 to
 4. 4. Apolyurethane according to claim 1 wherein component (c) is anisocyanate-reactive amine polyether (c)(i) or a combination of saidisocyanatereactive amine polyether (c)(i) with a smaller amount of afatty amido-amine (c)(ii) and/or an ammonium salt derivative of a fattyamido-amine (c)(iii).
 5. A polyurethane according to claim 1 whereincomponent (c) is an isocyanate-reactive amine polyether having amolecular weight of 200 to 600 and having the formula

    R[NR.sup.1 R.sup.2 ].sub.2

wherein R is a difunctional saturated C₂ -C₈ aliphatic group and R ¹ andR² are independently hydroxy-terminated polyethers containingexclusively polypropylene oxide units, or a combination of saidisocyanate-reactive amine polyether with a smaller amount of a fattyamido-amine (c)(ii) and/or an ammonium salt derivative of a fattyamido-amine (c)(iii).
 6. A rigid non-microcellular urethane-basedproduct containing a flame retardant prepared by the isocyanate additionreaction, at an isocyanate index of from 100 to 120 in the absence of ablowing agent, of an organic polyisocyanate with a storage-stableisocyanate-reactive composition comprising(a) 18 to 57 percent byweight, based on the total of components (a), (b), (c), (d), and (e), ofat least one isocyanate-reactive compound having a molecular weight of400 to 10,000 and a functionality of 2 to 7; (b) 28 to 67 percent byweight, based on the total of components (a), (b), (c), (d), and (e), ofat least one isocyanate-reactive compound having a molecular weight ofless than 399 and a functionality of 2 to 6; (c) 1.4 to 27 percent byweight, based on the total of components (a), (b), (c), (d), and (e), ofa tertiary amine or ammonium compound selected from the group consistingof(i) an isocyanate-reactive tertiary amine polyether having a molecularweight of from 100 to 1000 and having the formula

    R[NR.sup.1 R.sup.2 ].sub.m

wherein R is saturated or unsaturated C₂ -C₈ aliphatic or C₂ -C₈aliphatic substituted with --OH, --SH, or NHR^(a) wherein R^(a) is C₁-C₈ alkyl or C₂ -C₈ alkenyl; saturated or unsaturated C₅ -C₈cycloaliphatic or C₅ -C₈ cycloaliphatic substituted with C₁ -C₈ alkyl,C₂ -C₈ alkenyl, C₁ -C₈ alkylene, --OH, --SH, or NHR^(a) wherein R^(a) isalkyl or alkenyl; or five- or six-membered aromatic or heteroaromaticoptionally substituted with C₁ -C₈ alkyl, C₁ -C₈ alkoxy, halogen, cyano,nitro, C₁ -C₈ alkylene, --OH, --SH, or NHR^(a) wherein R^(a) is C₁ -C₈alkyl or C₂ -C₈ alkenyl; R¹ and R² are independently polyether groupsterminated with isocyanate-reactive groups selected from --OH, --SH, andNHR^(b) wherein R^(b) is C₁ -C₈ alkyl or C₂ -C₈ alkenyl; and m is aninteger of from 1 to 4; (ii) a fatty amido-amine; (iii) an ammonium saltderivative of a fatty amido-amine; and (iv) mixtures thereof; (d) 10 to38 percent by weight, based on the total of components (a), (b), (c),(d), and (e), of a flame retardant; p1 (e) 0.07 to 3.5 percent byweight, based on the total of components (a), (b), (c), (d), and (e), ofa catalyst selected from tertiary amines, organic metal compounds, andmixtures thereof; and (f) 0 to 15 percent by weight, based on the totalof components (a), (b), (c), (d), and (e), of additives.
 7. Aurethane-based non-microcellular product according to claim 6 whereincomponent (a) comprises a polyamine or aminocrotonate-terminatedpolyether and component (c) comprises 3 to 24 percent by weight of anisocyanate-reactive tertiary amine polyether (c)(i) and, optionally, 0.7to 14 percent by weight of a fatty amido-amine (c)(ii).
 8. Aurethane-based non-microcellular product according to claim 6 whereincomponent (a) comprises an isocyanate-reactive compound other than apolyamine or aminocrotonate-terminated polyether and component (c)comprises 3 to 24 percent by weight of an isocyanate-reactive tertiaryamine polyether (c)(i) and, optionally, 3 to 24 percent by weight of anammonium salt derivative of a fatty amido-amine (c)(iii).
 9. Anon-microcellular urethane-based elastomer containing a flame retardantprepared by the isocyanate addition reaction, at an isocyanate index offrom 90 to 110 in the absence of a blowing agent, of an organicpolyisocyanate with a storage-stable isocyanate-reactive compositioncomprising(a) 32 to 90 percent by weight, based on the total ofcomponents (a), (b), (c), (d), and (e), of at least oneisocyanate-reactive compound having a molecular weight of 400 to 10,000and a functionality of 2 to 7; (b) 0.7 to 38 percent by weight, based onthe total of components (a), (b), (c), (d), and (e), of at least oneisocyanate-reactive compound having a molecular weight of less than 399and a functionality of 2 to 6; (c) 1.4 to 27 percent by weight, based onthe total of components (a), (b), (c), (d), and (e), of a tertiary amineor ammonium compound selected from the group consisting of(i) anisocyanate-reactive tertiary amine polyether having a molecular weightof from 100 to 1000 and having the formula

    R[NR.sup.1 R.sup.2 ].sub.m

wherein R is saturated or unsaturated C₂ -C₈ aliphatic or C₂ -C₈aliphatic substituted with --OH, --SH, or NHR^(a) wherein R^(a) is C₁-C₈ alkyl or C₂ -C₈ alkenyl; saturated or unsaturated C₅ -C₈cycloaliphatic or C₅ -C₈ cycloaliphatic substituted with C₁ -C₈ alkyl,C₂ -C₈ alkenyl, C₁ -C₈ alkylene, --OH, --SH, or NHR^(a) wherein R^(a) isalkyl or alkenyl; or five- or six-membered aromatic or heteroaromaticoptionally substituted with C₁ -C₈ alkyl, C₁ -C₈ alkoxy, halogen, cyano,nitro, C₁ -C₈ alkylene, --OH, --SH, or NHR^(a) wherein R^(a) is C₁ -C₈alkyl or C₂ -C₈ alkenyl; R¹ and R² are independently polyether groupsterminated with isocyanate-reactive groups selected from --OH, --SH, andNHR^(b) wherein R^(b) is C₁ -C₈ alkyl or C₂ -C₈ alkenyl; and m is aninteger of from 1 to 4; (ii) a fatty amido-amine; (iii) an ammonium saltderivative of a fatty amido-amine; and (iv) mixtures thereof; (d) 20 to48 percent by weight, based on the total of components (a), (b), (c),(d), and (e), of a flame retardant; (e) 0.07 to 3.5 percent by weight,based on the total of components (a), (b), (c), (d), and (e), of acatalyst selected from tertiary amines, organic metal compounds, andmixtures thereof; and (f) 0 to 15 percent by weight, based on the totalof components (a), (b), (c), (d), and (e), of additives.
 10. Aurethane-based non-microcellular elastomer according to claim 9 whereincomponent (a) comprises a polyamine or aminocrotonate-terminatedpolyether and component (c) comprises 3 to 24 percent by weight of anisocyanatereactive tertiary amine polyether (c)(i) and, optionally, 0.7to 14 percent by weight of a fatty amido-amine (c)(ii).
 11. Aurethane-based non-microcellular elastomer according to claim 9 whereincomponent (a) comprises an isocyanate-reactive compound other than apolyamine or aminocrotonate-terminated polyether and component (c)comprises 3 to 24 percent by weight of an isocyanate-reactive tertiaryamine polyether (c)(i) and, optionally, 3 to 24 percent by weight of anammonium salt derivative of a fatty amido-amine (c)(iii).
 12. Apolyurethane containing a flame retardant applied to a substrate byspraying a mixture comprising an organic polyisocyanate and astorage-stable isocyanate-reactive composition mixed at an isocyanateindex of from 90 to 120 in the absence of a blowing agent, saidstorage-stable isocyanate-reactive composition comprising(a) 10 to 75percent by weight, based on the total of components (a), (b), (c), (d),and (e), of at least one isocyanate-reactive compound having a molecularweight of 400 to 10,000 and a functionality of 2 to 7; (b) 1 to 50percent by weight, based on the total of components (a), (b), (c), (d),and (e), of at least one isocyanate-reactive compound having a molecularweight of less than 399 and a functionality of 2 to 6; (c) 5 to 15percent by weight, based on the total of components (a), (b), (c), (d),and (e), of a tertiary amine or ammonium compound selected from thegroup consisting of(i) an isocyanate-reactive tertiary amine polyetherhaving a molecular weight of from 100 to 1000 and having the formula

    R[NR.sup.1 R.sup.2 ].sub.m

wherein R is saturated or unsaturated C₂ -C₈ aliphatic or C₂ -C₈aliphatic substituted with --OH, --SH, or NHR^(a) wherein R^(a) is C₁-C₈ alkyl or C₂ -C₈ alkenyl; saturated or unsaturated C₅ -C₈cycloaliphatic or C₅ -C₈ cycloaliphatic substituted with C₁ -C₈ alkyl,C₂ -C₈ alkenyl, C₁ -C₈ alkylene, --OH, --SH, or NHR^(a) wherein R^(a) isalkyl or alkenyl; or five- or six-membered aromatic or heteroaromaticoptionally substituted with C₁ -C₈ alkyl, C₁ -C₈ alkoxy, halogen, cyano,nitro, C₁ -C₈ alkylene, --OH, --SH, or NHR^(a) wherein R^(a) is C₁ -C₈alkyl or C₂ -C₈ alkenyl; R¹ and R² are independently polyether groupsterminated with isocyanate-reactive groups selected from --OH, --SH, andNHR^(b) wherein R^(b) is C₁ -C₈ alkyl or C₂ -C₈ alkenyl; and m is aninteger of from 1 to 4; (ii) a fatty amido-amine; (iii) an ammonium saltderivative of a fatty amido-amine; and (iv) mixtures thereof; (d) 5 to55 percent by weight, based on the total of components (a), (b), (c),(d), and (e), of a flame retardant; (e) 0.01 to 1.5 percent by weight,based on the total of components (a), (b), (c), (d), and (e), of acatalyst selected from tertiary amines, organic metal compounds, andmixtures thereof; and (f) 0 to 15 percent by weight, based on the totalof components (a), (b), (c), (d), and ( e ), of additives.
 13. Apolyurethane according to claim 12 wherein component (c) comprises 6 to10 percent by weight of an isocyanate-reactive tertiary amine polyether(c)(i).